JP2002526637A - Method for producing middle distillate and middle distillate produced by the method - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to cold filter plugging points (CFPP), measured according to IP method (309), and middle distillates having a high cetane number, and to such cold distillates. The present invention relates to a method for producing a distillate. In particular, the present invention is that the reaction of CO and H _2, typically Fischer - about middle distillate which is mainly produced from paraffinic synthetic material produced by Tropsch (FT) process. The middle distillate of the present invention is mainly isoparaffinic and is isoparaffin branched with methyl, ethyl and / or propyl. The present invention further provides a diesel fuel composition comprising the middle distillate of the present invention. The method for preparing this middle distillate is also included in the present invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to middle distillates having good cold flow properties, such as the cold filter plugging point (CFPP) measured according to IP method 309, and a high cetane number, and a process for producing such distillates. In particular, the present invention is that the reaction of CO and H _2, typically Fischer - about middle distillate which is mainly produced from paraffinic synthetic material produced by Tropsch (FT) process.

[0002]

[Prior art]

Background to the Invention Wax-like products of FT hydrocarbon synthesis processes, particularly those of cobalt and / or iron based catalytic processes, contain high proportions of normal paraffins. The first FT product is
Poor cold flow properties, as is well known, make cold flow properties important, making it difficult to use such products, for example, in lubricating oil bases and jet fuels. The cold flow properties of middle distillates, such as jet fuels, can be improved by increasing the paraffin branching of the distillate in the appropriate boiling range and by hydrocracking and hydroisomerizing heavy components. This is known in the art. However, hydrocracking produces small amounts of gas and light products, which reduce the yield of valuable distillates. Incentives remain for methods to maximize middle distillates obtained from FT waxes having good refrigeration properties and high cetane numbers. The middle distillate of the present invention is produced from a high paraffinic syncrude obtained from a syngas via a reaction such as an FT reaction. This FT first product is
It covers a wide range of hydrocarbons from methane to species with a molecular weight of about 1400, mainly containing paraffinic hydrocarbons and very small amounts of other species such as olefins and oxygenates. The prior art US Pat. No. 5,378,348 discloses that by hydrotreating and isomerizing the product from a Fischer-Tropsch reactor, the freezing point due to the isoparaffinic nature of the fuel
A jet fuel of 34 ° C. or less can be obtained. If the branching of the product is improved compared to the waxy paraffin feed, the cetane number (burning) will be lower than normal (straight chain) paraffins, ie the increased branching will be due to the paraffinic hydrocarbon fuel Decrease the cetane number of

[0003]

[Problems to be solved by the invention]

It has now surprisingly been found by the applicant that a hydrotreated middle distillate, for example diesel, is provided with a high cetane number as well as good cold flow properties. The middle distillate of the present invention may be used on its own or in a mixture to improve the quality of other fuels that do not meet current and / or proposed stricter fuel quality specifications.

[0004]

[Means for Solving the Problems]

SUMMARY OF THE INVENTION Accordingly, a first aspect of the present invention provides a process for producing middle distillates or distillate blends, such as diesel, having high cetane numbers and good cold flow properties. This synthetic middle distillate fraction may have more than 50%, mainly isoparaffins branched by methyl and / or ethyl and / or propyl. Mass ratio profile slope of synthetic middle distillate fraction isoparaffins pair n- paraffins, about 1 for C _8: 1 with respect to C ₁₅ from 8.54: increased to 1, and C ₁₈ for about 3: 1 to decrease again May be. Typically, the fraction of synthetic middle distillate fractions in the carbon number range of C ₁₀ -C ₁₈ is higher than the C ₈ -C ₉ fraction of the synthetic middle distillate fraction isoparaffins to-n- paraffins ratio Have. C ₁₀ -C ₁₈ fraction of isoparaffins versus n- paraffins mass ratio is 1:
It may be 1 to 9: 1. The weight ratio of isoparaffins pair n- paraffins to synthetic middle distillate fraction C ₁₅ fraction of 8.54: 1. Middle distillate fraction C ₁₉ ~
C ₂₄ fraction is isoparaffin-to n- paraffins narrow mass ratio range, 3.3: 1 to 5: 1, typically 4: 1 to 4.9: 1. The mass ratio of isoparaffin to n-paraffin may be adjusted by controlling the mixing ratio of the hydrocrackate of the synthetic middle distillate fraction to the straight run components. Thus, C ₁₀ -C ₁₈ fraction of isoparaffins pairs with 30% straight run component n
The paraffin mass ratio may be from 1: 1 to 2: 5: 1. C _{1 0} -C ₁₈ fraction mass ratio of isoparaffins pair n- paraffins having 20% straight run component, 1.5: 1 to 3: 5: 1. The weight ratio of isoparaffins pair n- paraffins C ₁₀ -C ₁₈ fraction with 10% straight run component, 2.3: 1 to 4.3: 1. C ₁₀ -C ₁₈ fraction mass ratio of isoparaffins pair n- paraffins having substantially only hydrocracked components, 4: 1-9
: 1. At least certain isoparaffins of the middle distillate fraction may be methyl-branched. Typically, at least certain isoparaffins may be dimethyl-branched. At least 30% (by weight) of the isoparaffins are monomethyl branched. However, certain isoparaffins may be ethyl-branched.

Table A: Comparison of branching properties of mixtures of SR, HX and SPD diesel In the table, SPD: Sasol slurry phase distillate SR: Straight run HX: Hydrocracking

Table B: Properties of mixtures of SR and RX diesel

According to a further aspect of the present invention there is provided a synthetic middle distillate having a cetane number higher than 70 and a CFPP according to IP309 lower than −20 ° C., said distillate having the above isoparaffin content. In some embodiments, the synthetic middle distillate fraction is a FT product. The invention extends to a diesel fuel composition comprising between 10% and 100% of said middle distillate fraction. Typically, the diesel fuel composition may contain 0-90% of one or more other diesel fuels. The diesel fuel composition may include at least 20% of the middle distillate fraction, the composition having a cetane number greater than 47 and a CFPP according to IP309 below -22 ° C. This diesel fuel composition
The middle distillate may comprise at least 30%, and the composition has a cetane number greater than 50 and a CFPP according to IP309 below -22 <0> C. The diesel fuel composition may comprise at least 50% of middle distillate, the composition having a cetane number greater than 52 and a CFPP according to IP309 below -25C. The diesel fuel composition may comprise at least 70% of middle distillate, the composition having a cetane number greater than 60 and a CFPP according to IP309 below -30C. The diesel fuel composition may contain 0-10% of additives. This additive
A lubricity improver may be included. This lubricity improver is 0-0.5% based on the composition.
, Typically from 0.00001% to 0.05% of the composition. In some embodiments, the lubricity enhancer comprises 0.008% to 0.02% of the composition. This diesel fuel composition may be used as another diesel fuel, such as crude oil-derived diesel, for example, US2-D grade (low sulfur No.2-D grade for diesel fuel as specified in ASTM D 975-94) and / or CARB (California Air Resources Board 1993 standard) may include diesel fuel.

[0008] In accordance with yet another aspect of the present invention, there is provided a method for producing a synthetic middle distillate having a cetane number greater than 70, comprising: (a) separating the product obtained from the synthesis gas via the FT synthesis reaction into one or more heavy fractions and one or more light fractions; (b) mainly separating the middle distillate Catalytically treating said heavy fraction under the conditions which occur; (c) removing the middle distillate product of step (b) from the light product fraction and heavy product produced in step (b). Separating from the fractions; and (d) mixing the middle distillate fraction obtained in step (c) with at least a part of one or more light fractions of step (a) or a product thereof. . The catalyst treatment in step (b) may be a hydrotreating step, for example, hydrocracking. The process for producing a synthetic middle distillate comprises, prior to step (d), one or more steps (
It may comprise one or more additional steps of fractionating at least some of the light fraction of a) or its products. The process for producing a synthetic middle distillate comprises, prior to step (d), an additional step of hydrotreating at least some of the light fraction of step (a) or of its products. May be included. The heavy fraction of one or more steps (a) is about 2
It may have a boiling point higher than 70 ° C and may be higher than 300 ° C. One or more light fraction may have a boiling point in the range from C ₅ up to the boiling point of the heavy fraction, typically 160 ° C.
It is in the range of -270 ° C. The product of step (d) may be boiled in the range from 100C to 400C. The product of step (d) may boil in the range of 160C to 370C. Step (d)
May be diesel fuel. The product of step (d) is at -20C
It may have a lower, typically less than −30 ° C., even less than −35 ° C. CFPP. The product of step (d) comprises a volume fraction of the middle distillate fraction obtained in step (c) and at least one light fraction of step (a) or at least a part of the product. At 1: 1 to 9: 1, typically 2: 1 to 6: 1, and in one embodiment at a volume ratio of 84:16.

[0009] The present invention further extends to a method of producing middle distillate fuel from an FT first product, comprising primarily long chain linear paraffins. In this method, the wax product from the FT method has at least two fractions,
It is separated into heavy and at least one light fraction. Subjecting the light components to mild catalytic hydrogenation to remove heteroatoms, e.g., oxygen, saturate the olefin,
Thereby producing materials useful as naphtha, solvents, diesel and / or mixed components therefor. The heavy fraction may be catalytically hydrotreated without first hydrotreating to produce a product having good cold flow properties. This hydrotreated heavy fraction is mixed with all or part of the hydrogenated and / or non-hydrogenated light fraction to obtain, after fractionation, a diesel fuel characterized by naphtha and a high cetane number. . Suitable catalysts for the hydroprocessing step are commercially available and are selected for the improved quality of the desired end product.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention describes the conversion of a first FT product to naphtha and middle distillates, for example, to a diesel as described above having a high cetane number greater than 70 and having better cold flow properties. I do. The FT process is used industrially to convert syngas from coal, natural gas, biomass or heavy oil streams to hydrocarbons ranging from methane to species with molecular weights greater than 1400. While the main products are linear paraffinic materials, other species, such as branched paraffins, olefins and oxygenated components form part of the product slate. Exactly the product slate depends on the reactor configuration, operating conditions and the catalyst used, which is, for example, Catal. Rev.-Sci. Eng.,
23 (1 & 2), pp. 265-278 (1981). Preferred reactors for the production of heavier hydrocarbons are slurry beds or tubular fixed bed types. Here, typical operating conditions are 160-280 ° C., in some cases 210-2
60 ° C., and 1.8-5.0 Pa (18-50 Bar), and in some cases 2.0-3.0 Pa (20-30 Ba)
r). Preferred active metals in the catalyst are iron, ruthenium or cobalt. While each catalyst provides its own unique product slate, in all cases this product slate is a somewhat waxy, highly paraffinic material that needs to be further refined to a useful product including. The FT product is the final product,
For example, it may be converted to a range of middle distillate, gasoline, solvent, lubricating oil base and the like.
Such a transformation, which typically comprises a range of methods such as hydrocracking, hydrotreating and distillation, is called an FT workup method.

The FT work-up process of the present invention uses a feed stream consisting of C ₅ and higher hydrocarbons derived from the FT process. The feed is separated into at least two fractions, a heavier fraction and at least one light fraction. The cut point of the two fractions is preferably below 300 ° C and typically below about 270 ° C. The table below gives a typical composition of the two fractions within ± 10% accuracy. Table 1-Typical Fischer-Tropsch products after separation into two fractions (% by volume) The> 270 ° C fraction (designated as wax) contains a significant amount of hydrocarbon material, which boils above the range of standard diesel. Diesel boiling range is 160-3
Considering 70 ° C, all substances heavier than about 370 ° C are often hydrotreated,
It means that it needs to be converted to lighter substances, for example by a catalytic method called hydrocracking. The catalyst for this step is of the bifunctional type; that is, it contains active sites for cracking and hydrogenation. Catalyst metals active for hydrogenation include those containing a Group VIII noble metal, such as platinum or palladium, or a Group VIII sulfide base metal such as nickel or cobalt, with or without a Group VI metal such as molybdenum. The support for this metal can be any refractory oxide, such as silica, alumina, titania, zirconia, vanadia, and other
The oxides of groups III, IV, VA and VI may be themselves or in combination with other poorly soluble oxides. Alternatively, the support may consist partially or wholly of zeolite. However, the preferred support in the present invention is amorphous silica alumina.

[0012] The process conditions for hydrocracking can be varied over a wide range and are usually chosen after extensive experimentation to optimize middle distillate yields. In this regard, it is noteworthy that there are trade-offs between conversion and selectivity, as in many chemical reactions. Very high conversions result in high gas yields and low distillate fuel yields. Therefore, it is important to fine-tune the process conditions to limit the conversion of hydrocarbons at> 370 ° C. Table 2 describes preferred conditions. Table 2:-Typical hydrocracking process conditions Nevertheless, during the hydrocracking process, all of the material at> 370 ° C. in the feedstock can be converted by recycling the unconverted portion.

As is evident from Table 1, the majority of the fraction boiling below 270 ° C. is already within the typical boiling range of diesel, ie 160-370 ° C. This fraction may or may not undergo hydrogen treatment. Heteroatoms are removed by hydrogen treatment; and
Unsaturated compounds are hydrogenated. Hydroprocessing is any catalyst that has a hydrogenation action,
For example, well-known industrial processes that are also catalyzed by Group VIII noble metals or sulfide-based metals or Group VI metals, or combinations thereof. Preferred supports are alumina and silica. Table 3 describes typical operating conditions for the hydrotreating process.

Table 3-Typical hydroprocessing process conditions While the hydrotreated fraction may be fractionated into a paraffinic material useful as a solvent, the Applicant has now determined that the hydrotreated fraction can be directly combined with the product obtained from the hydrocracked wax. It has been found that they may be mixed. Applicants have found that despite this being able to hydroisomerize the material contained in the condensate stream, this results in a small but significant loss of diesel boiling range material over lighter material. In addition, they have found that isomerization results in the formation of branched isomers, lowering the cetane number below that of the corresponding normal paraffin.

[0015] The combination of highly linear paraffin obtained from the <270 ° C fraction and predominantly branched paraffin obtained from the> 270 ° C fraction results in a superior diesel. Important parameters for the FT workup method are maximizing product yield, product quality and cost. When the proposed method scheme is simple and cost-effective, it provides a high performance diesel with a cetane number> 70 and a good yield of naphtha. Indeed, the process of the present invention can provide a quality that is not traditionally diesel, which is characterized by a unique combination of high cetane number and excellent cold flow properties. This is believed to be associated with a low degree of isomerization in the 160-270 ° C fraction of diesel and, conversely, a high degree of isomerization in the 270-370 ° C fraction of diesel. Light boiling range of diesel (fraction of 160-270 ℃) and diesel (270 ℃ -370 ℃)
The total amount of isomers in the heavier range of is shown in Table 4 below.

Table 4-Isoparaffins of the mid-fraction: n-paraffins The relatively high percentage of normal paraffins in the light boiling range contributes to the high cetane number of diesel fuel without affecting the cold flow properties. On the other hand, in the heavy range of diesel, branching is of the utmost importance, because straight chain hydrocarbons in this range have very poor cooling flow properties, and in some cases,
This is because crystallization is performed. Therefore, the amount of isoparaffin in this range is
It is maximized during hydroprocessing under the process conditions described herein. It is precisely this unique composition of the synthetic fuel that leads to the unique properties of the fuel, which is directly generated by the method of working the FT work-up method of the present invention.

The Applicant has further found that, from a fuel quality point of view, it is not necessary to hydrotreat the <270 ° C. fraction, but to add said fraction directly to the product of hydrocracking the wax. This will include oxygenates and unsaturated compounds in the final diesel, but fuel specifications usually allow this. Avoiding the need for condensate hydroprocessing results in significant capital and operating cost savings. The described FT workup method of FIG. 1 may be linked in many arrangements.
Applicants view these as the use of a technique known as Process Synthesis Optimization. However, specific process conditions for the work up of the FT first product,
The possible process sequences outlined in Table 5 were obtained after extensive and tedious experimentation and design.

Table 5-Arrangement of possible Fischer-Tropsch product work-up methods Numbers: symbols of FIG. 1. FT: Fischer-Tropsch. The basic process is outlined in FIG. Syngas, a mixture of hydrogen and carbon monoxide, enters the FT reactor 1 where the synthesis gas is converted to hydrocarbons by the FT method. The lighter FT fraction is collected in line 7 and passes or does not pass through rectification column 2 and hydrotreater 3. The product 9 from the hydrotreater may be separated in the rectifier 4 or, alternatively, may be mixed with the hydrocracker product 16 and sent to the general rectifier 6 You may be. The wax-like FT fraction is collected in the line 13 and sent to the hydrocracker 5. If fraction 2 is taken into account, bottom fraction 12 is further sent to hydrocracking unit 5. The product 16 is separated as it is or mixed with the light fraction 9a in the rectification column 6. According to the method scheme, the light product fraction, naphtha 19, is obtained from rectification column 6 or by mixing equivalent fractions 10 and 17. This is a C ₅ to 160 ° C. fraction useful as naphtha. A somewhat heavier fraction, synthetic diesel 20, can be obtained from rectification column 6 or by a similar method of mixing equivalent fractions 11 and 18. This fraction is recovered as a 160-370 ° C. fraction useful in diesel. Heavy unconverted material 2 from rectification column 6
1 is recycled to the hydrocracker 5 for extinction. Alternatively, the residue may be used for production of a synthetic lubricating oil base. A small amount of C ₁ -C ₄ gas is further separated in the rectification column 6. The following examples further illustrate the invention.

[0019]

【Example】

Example 1 A commercially available hydrocracking catalyst is used for the hydrocracking of a non-hydrogenated FT hydrocarbon fraction at an initial boiling point of about 280 ° C. Active metals on the catalyst include cobalt and molybdenum, and the support is amorphous silica-alumina. The operating conditions are a temperature of 375-385 ° C., a pressure of 7.0 Pa (70 bar) and a hydrogen flow rate of 1500 m ³ _n / m ^3.
It was a supply. The experiment was performed in a pilot plant. The conversion of> 370 ° C material to light material is in the range of 65-80%. Diesel component A is obtained after fractionation of the reactor product. Table 1 shows the characteristics of this diesel component.

Example 2 A non-hydrogenated FT hydrocarbon fraction having a final boiling point of about 285 ° C. and an alcohol content of about 4.3% by weight, expressed as n-hexanol and using a commercially available catalyst Strictly hydrogenated. Active metals on the catalyst include molybdenum and cobalt, and the support is alumina. The operating conditions are a temperature of about 250 ° C. and a pressure of 6.8.
Pa (68 bar) and hydrogen flow rate were 1070 m ³ _n / m ³ . The experiments were performed in a commercial scale fixed bed reactor. Diesel components B and C are obtained after reactor feed and fractionation of the reactor product, respectively. Table 6 shows the characteristics of these diesel components. Table 6: Diesel mixed components

Example 3 A diesel fraction obtained by hydrocracking a heavy FT material (component A) was mixed with a hydrogenated light FT material (component B) in a volume ratio of 84:16. The properties of the final blend are shown in Table 7 as Blend I. Those skilled in the art will appreciate that Blend I may be used as a mixed feedstock as well as itself. Due to the combination of high cetane number (greater than 70) and excellent cold flow properties (CFPP substantially better than −20 ° C.), Blend I
It is an ideal mixed supply stock for upgrading crude oil-derived diesel.

Example 4 A diesel fraction obtained by hydrocracking a heavy FT material (component A) was directly mixed with a lighter unhydrogenated FT material (component C) in a volume ratio of 84:16. . The properties of the final blend are shown in Table 7 as Blend II. As in Example 3, Blend II may be used as a mixed feedstock as well as itself. In addition to a high cetane number (greater than 70) and excellent cold flow properties (CFPP substantially better than -20 ° C), Blend II contains alcohol and small amounts of many oxides, the level of Depends on the mixing ratio used. Table 7: Diesel blend

Example 5 The diesel blend I of Example 3 was prepared using the desired cetane number and CF as shown in Table 8.
Mixed with US2-D grade diesel with PP properties, the following charts 1 and 2
I got Table 8: Performance characteristics of Sasol SPD diesel, 2D diesel and blends

[Brief description of the drawings]

FIG. 1 is a schematic diagram of the FT workup method of the present invention.

[Explanation of symbols]

 1: FT reactor 2: rectification column 3: hydrotreating unit 4: rectification column 5: hydrocracking unit 6: rectification column 7: line 9 (9a): product 10: fraction 11: fraction 12 : Bottom fraction 13: line 17: fraction 18: fraction 19: naphtha 20: synthetic diesel 21: unconverted material

[Procedure amendment]

[Submission date] January 7, 2002 (2002.1.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

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[0001]

The present invention relates to cold filter plugging points (CFPP) measured according to IP method 309, and to middle distillates having a high cetane number, and to such distillates. The present invention relates to a method for producing a product. In particular, the present invention is that the reaction of CO and H _2, typically Fischer - about middle distillate which is mainly produced from paraffinic synthetic material produced by Tropsch (FT) process.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

BACKGROUND OF THE INVENTION Wax-like products of FT hydrocarbon synthesis processes, especially those of cobalt and / or iron based catalytic processes, contain a high proportion of normal paraffins. The first FT product is
Poor cold flow properties, as is well known, make cold flow properties important, making it difficult to use such products, for example, in lubricating oil bases and jet fuels. The cold flow properties of middle distillates, such as jet fuels, can be improved by increasing the paraffin branching of the distillate in the appropriate boiling range and by hydrocracking and hydroisomerizing heavy components. This is known in the art. However, hydrocracking produces small amounts of gas and light products, which reduce the yield of valuable distillates. Incentives remain for methods to maximize middle distillates obtained from FT waxes having good refrigeration properties and high cetane numbers. The middle distillate of the present invention is produced from a high paraffinic syncrude obtained from a syngas via a reaction such as an FT reaction. This FT first product is
It covers a wide range of hydrocarbons from methane to species with a molecular weight of about 1400, mainly containing paraffinic hydrocarbons and very small amounts of other species such as olefins and oxygenates. The prior art US Pat. No. 5,378,348 discloses that by hydrotreating and isomerizing the product from a Fischer-Tropsch reactor, the freezing point due to the isoparaffinic nature of the fuel
A jet fuel of 34 ° C. or less can be obtained. If the branching of the product is improved compared to the waxy paraffin feed, the cetane number (burning) will be lower than normal (straight chain) paraffins, ie the increased branching will be due to the paraffinic hydrocarbon fuel Decrease the cetane number of Further, WO 97/14769 has excellent lubricity, oxidation stability and high cetane number,
Produced from a non-shifted Fischer-Tropsch process and at> 95% by weight,
Open diesel fuel with paraffin with iso-normal ratio of 0.3 to 3.0
Show. This refers to the effect of branching on cold flow properties or cetane number
It has not been. Furthermore, WO 98/34998 discloses a process for the production of additive compositions, in particular Fischer-Trop
Cetane number or middle distillate diesel fuel via lubrication
Useful for. This additive provides the product of the Fischer-Tropsch reaction.
Separation into low boiling 371 ° C fraction and high boiling fraction, hydrogenation of high boiling fraction to low boiling fraction
By mixing the low-boiling fraction and the high-boiling fraction hydroisomerized,> 50% by mass
To produce additives having> 16% by weight of soparaffins with C16 to C20 paraffins.
And is prepared by This disclosure has good cold flow properties and high cetane number.
Do not disclose that the diesel fuel can be produced, disclose only additives, and
This disclosure began to lose material from the diesel boiling range to lighter materials
And the hydroisomerization of the high boiling fractions, which will form branched isomers,
This translates into a lower cetane rating corresponding to n-paraffins. This disclosure is
Furthermore, it does not address the issue of cold flow properties, as well as the issue of cetane number.

[Procedure amendment 4]

[Document name to be amended] Statement

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[0004]

SUMMARY OF THE INVENTION Accordingly, according to a first aspect of the present invention, there is provided a process for producing middle distillates or distillate blends, such as diesel, having high cetane numbers and good cold flow properties. Is done. This synthetic middle distillate fraction may have more than 50%, mainly isoparaffins branched by methyl and / or ethyl and / or propyl. Synthesis middle distillate fraction may include lighter more C ₁₆ than 50 wt% paraffins. Mass ratio profile slope of synthetic middle distillate fraction isoparaffins pair n- paraffins, about 1 for C _8: 1 with respect to C ₁₅ from 8.54: increased to 1, and C ₁₈ for about 3: 1 to decrease again May be. Typically, the fraction of synthetic middle distillate fractions in the carbon number range of C ₁₀ -C ₁₈ is higher than the C ₈ -C ₉ fraction of the synthetic middle distillate fraction isoparaffins to-n- paraffins ratio Have. C ₁₀ -C ₁₈ fraction of isoparaffins versus n- paraffins mass ratio is from 1: 1 to 9: 1. The weight ratio of isoparaffins pair n- paraffins to synthetic middle distillate fraction C ₁₅ fraction of 8.54: 1. Middle distillate fraction C ₁₉ -C ₂₄ fraction of isoparaffin-to-n- paraffins narrow mass ratio range, 3.3: 1 to 5: 1, typically 4: 1 to 4.9: even 1 Good. The mass ratio of isoparaffin to n-paraffin may be adjusted by controlling the mixing ratio of the hydrocrackate of the synthetic middle distillate fraction to the straight run components. Therefore, the weight ratio of C ₁₀ -C ₁₈ fraction of isoparaffins pair n- paraffins having 30% straight run component, 1: 1 to 2.5: 1. The weight ratio of isoparaffins pair n- paraffins C ₁₀ -C ₁₈ fraction with 20% of the straight run component 1.
5: 1 to 3.5 : 1. The weight ratio of isoparaffins pair n- paraffins C ₁₀ -C ₁₈ fraction with 10% straight run component, 2.3: 1 to 4.3: 1. The mass ratio of substantially isoparaffin-to n- paraffins C ₁₀ -C ₁₈ fraction with only decomposed components hydrogenation, 4: 1-9: 1. At least certain isoparaffins of the middle distillate fraction may be methyl-branched. Typically, at least certain isoparaffins may be dimethyl-branched. At least 30% of isoparaffins (
Mass) is a monomethyl branch. However, certain isoparaffins may be ethyl-branched.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Invention The owner Prince Mark Jean South Africa Seysolburg 9570 Waterson Street 61 (72) Inventor Dewet Edward Watermayer South Africa Vanderbilt Park 1911 Beethoven Street 24 F-term (reference) 4H013 AA01

Claims (65)

[Claims] 1. A synthetic middle distillate fraction containing more than 50% of isoparaffins, characterized in that the isoparaffins are mainly methyl and / or ethyl and / or propyl branches. Middle distillate fraction. 2. A synthetic middle distillate fraction mass ratio profile of isoparaffin-to-n- paraffins slope, approximately for C ₈ 1: 1 with respect to C ₁₅ from 8.54: increased to 1, and about 3 for C ₁₈ 2. The synthetic middle distillate fraction according to claim 1, which again decreases to 1: 1. 3. The isoparaffin to n-paraffin ratio wherein the fraction of the synthetic middle distillate fraction in the carbon number range of C _{10 to} C ₁₈ is higher than the C _{8 to} C ₉ fraction of the synthetic middle distillate fraction. 3. The synthetic middle distillate fraction according to claim 1, comprising: 4. The mass ratio of isoparaffin to n-paraffin in the C ₁₀ -C ₁₈ fraction is 1: 1.
4. The synthetic middle distillate fraction according to claim 2, wherein the ratio is 1 to 9: 1. Weight ratio of 5. A isoparaffin-to n- paraffins, to synthetic middle distillate fraction C ₁₅ fraction of about 8.54: 1, the synthetic intermediate according to any one of claims 2-4 Distillate fraction. 6. The process according to claim 2, wherein the C ₁₉ -C ₂₄ fraction of the middle distillate fraction has a narrow mass ratio of isoparaffin to n-paraffin of 3.3: 1 to 5: 1. , A synthetic middle distillate fraction. 7. The process according to claim 2, wherein the C ₁₉ -C ₂₄ fraction of the middle distillate fraction has a narrow mass ratio range of isoparaffin to n-paraffin of 4: 1 to 4.9: 1. , A synthetic middle distillate fraction. 8. The method according to claim 1, wherein the mass ratio of isoparaffin to n-paraffin can be adjusted by controlling the mixing ratio of hydrocracked product to straight-run component of the synthetic middle distillate fraction. A synthetic intermediate distillate fraction according to the above. 9. Isoparaffins versus n-parts in a C ₁₀ -C ₁₈ fraction having a 30% straight-run component.
9. The synthetic middle distillate fraction according to claim 8, wherein the mass ratio of paraffin is from 1: 1 to 2: 5: 1. 10. An isoparaffin pair in a C ₁₀ -C ₁₈ fraction having a straight-run component of 20%.
9. The synthetic middle distillate fraction according to claim 8, wherein the mass ratio of n-paraffin is from 1.5: 1 to 3: 5: 1. 11. An isoparaffin pair in a C ₁₀ -C ₁₈ fraction having a 10% straight-run component.
9. The synthetic middle distillate fraction according to claim 8, wherein the mass ratio of n-paraffin is from 2.3: 1 to 4.3: 1. 12. The method according to claim 8, wherein the mass ratio of isoparaffins to n-paraffins in the C ₁₀ -C ₁₈ fraction having substantially only the hydrocracked components is from 4: 1 to 9: 1. Of the synthetic middle distillate. 13. The middle distillate fraction according to claim 1, wherein at least certain isoparaffins are methyl branches. 14. At least certain isoparaffins are dimethyl-branched.
An intermediate distillate fraction according to any of the preceding claims. 15. The middle distillate fraction according to claim 1, wherein at least 30% by weight of the isoparaffins are monomethyl branches. 16. The middle distillate fraction according to claim 1, wherein at least certain isoparaffins are ethyl branches. 17. The mass ratio of isoparaffin to n-paraffin is from about 1: 1 to about 12: 1.
The middle distillate fraction according to any one of claims 1 to 16, wherein 18. The synthetic middle distillate fraction according to claim 17, wherein the mass ratio of isoparaffin to n-paraffin is from about 2: 1 to about 6: 1. 19. The synthetic middle distillate fraction according to claim 18, wherein the mass ratio of isoparaffin to n-paraffin is 4: 1. 20. A process according to claim 1, having a light fraction in the boiling range from 160 ° C. to 270 ° C., wherein the mass ratio of isoparaffin to n-paraffin is from 1: 2 to 4: 1. The described synthetic middle distillate fraction. 21. The synthetic middle distillate fraction according to claim 20, having a light fraction in the boiling range from 160 ° C. to 270 ° C. and a mass ratio of isoparaffin to n-paraffin of 2.2: 1. . 22. A process according to claim 1, having a heavy fraction in the boiling range from 270 ° C. to 370 ° C., wherein the mass ratio of isoparaffin to n-paraffin is from 4: 1 to 14: 1. , A synthetic middle distillate fraction. 23. The synthetic middle distillate fraction according to claim 22, having a heavy fraction in the boiling range of 270 ° C. to 370 ° C., wherein the mass ratio of isoparaffin to n-paraffin is 21: 2. Minutes. 24. C according to IP309, having a cetane number higher than 70 and an IP309 lower than -20 ° C.
A synthetic middle distillate fraction having FPP, characterized in that said distillate has an isoparaffin content substantially as described in any of claims 1 to 23. Distillate. 25. The synthetic middle distillate fraction according to claim 1, wherein the synthetic distillate is derived from one or more FT first products. 26. The middle distillate fraction according to any one of claims 1 to 25,
A diesel fuel composition comprising １００100%. 27. The composition of claim 26, comprising 0 to 90% of one or more other diesel fuels.
2. The diesel fuel composition according to item 1. 28. The diesel fuel composition according to claim 26, comprising 20-80% of one or more other diesel fuels. 29. The diesel fuel composition according to claim 26, comprising at least 20% of a middle distillate fraction, having a cetane number higher than 47 and a CFPP according to IP309 below -22 ° C. 30. The diesel fuel composition according to claim 26, comprising at least 30% of the middle distillate fraction and having a CFPP according to IP309 below 50 and a cetane number below -22 ° C. 31. The diesel fuel composition according to claim 26, comprising at least 50% of a middle distillate fraction and having a CFPP according to an IP309 below 52 and a cetane number below -25 ° C. 32. The diesel fuel composition according to claim 26, comprising at least 70% of a middle distillate fraction and having a CFPP according to IP309 below 60 ° C. and below -30 ° C. 33. The diesel fuel composition according to claim 26, comprising 0 to 10% of an additive. 34. The diesel fuel composition according to claim 33, wherein said additive comprises a lubricity improver. 35. The diesel fuel composition according to claim 34, wherein said lubricity improver is contained in an amount of 0 to 0.5% based on the composition. 36. The diesel fuel composition according to claim 35, wherein said lubricity improver is contained in the composition at 0.00001% to 0.05%. 37. The diesel fuel composition according to claim 36, comprising 0.008% to 0.02% of the lubricity improver based on the composition. 38. The diesel fuel composition according to claim 28, wherein one of the other diesel fuels is a US 2-D grade diesel fuel. 39. The diesel fuel composition according to claim 28, wherein one of the other diesel fuels is a CARB grade diesel fuel. 40. A process for producing a synthetic middle distillate having a cetane number higher than 70, comprising: (a) converting the product obtained from syngas via an FT synthesis reaction to one or more Separating a heavy fraction and one or more light fractions; (b) catalytically treating the heavy fraction under conditions that mainly produce middle distillates;
(c) separating the middle distillate product of step (b) from the light and heavy product fractions formed in step (b); and (d) obtained in step (c). Mixing the middle distillate fraction and at least a part of one or more light fractions of step (a) or products thereof, a process for producing a synthetic middle distillate. 41. The process according to claim 4, wherein the catalyst treatment in step (b) is a hydrotreating step.
0. The process for producing a synthetic middle distillate according to 0. 42. The method according to claim 4, which comprises, before step (d), one or more additional steps for fractionating at least some of the light fraction of step (a) or of its products.
42. The method for producing a synthetic middle distillate according to 0 or 41. 43. An additional step of hydrotreating at least some of one or more of the light fractions of step (a) or products thereof prior to step (d).
3. The method for producing a synthetic intermediate distillate according to any one of 2. 44. The heavy fraction of one or more steps (a) boils at about 270 ° C.
A method for producing a synthetic middle distillate according to any one of claims 30 to 43. 45. The synthetic middle distillate of claim 44, wherein the heavy fraction of one or more steps (b) has an isoparaffin to n-paraffin mass ratio of 4: 1 to 14: 1. Production method. 46. The process for producing a synthetic middle distillate according to claim 45, wherein the heavy fraction of one or more steps (b) has a mass ratio of isoparaffin to n-paraffin of 21: 2. 47. The heavy fraction of one or more steps (a) boils at about 300 ° C.
A method for producing a synthetic intermediate distillate according to any one of claims 30 to 46. 48. One or more lighter fraction, boiling in the range of the boiling point of C ₅ ~ heavy fraction, a method of producing synthetic middle distillate as claimed in any one of claims 30 to 47. 49. The process for producing a synthetic middle distillate according to any one of claims 30 to 48, wherein one or more light fractions boils in the range of 160 ° C to 270 ° C. 50. The method of claim 50, wherein the one or more light fractions comprises a 1: 2 to 4: 1 isoparaffin pair.
50. The method for producing a synthetic middle distillate according to claim 48 or 49, wherein the method has an n-paraffin mass ratio. 51. The process for producing a synthetic middle distillate according to any of claims 48 to 50, wherein the one or more light fractions have a 2.2: 1 mass ratio of isoparaffin to n-paraffin. 52. The process for producing a synthetic middle distillate according to claim 40, wherein the product of step (d) boils in the range of 100 ° C. to 400 ° C. 53. The process for producing a synthetic middle distillate according to claim 40, wherein the product of step (d) boils in the range of 160 ° C. to 370 ° C. 54. The product of claim 40, wherein the product of step (d) is a diesel fuel.
3. The method for producing a synthetic intermediate distillate according to any one of 3. 55. The process for producing a synthetic middle distillate according to any of claims 40 to 54, wherein the product of step (d) has a CFPP lower than -20 ° C. 56. The process for producing a synthetic middle distillate according to claim 54, wherein the product of step (d) has a CFPP of less than -30 ° C. 57. The process for producing a synthetic middle distillate according to claim 56, wherein the product of step (d) has a CFPP of less than -35 ° C. 58. The product of step (d) comprising the middle distillate fraction obtained in step (c) and one or more light fractions of step (a) or at least a part of the product thereof. Of the synthetic middle distillate according to any of claims 40 to 57, obtained by mixing at a selected volume ratio to provide a diesel fuel having the required specifications. 59. The product of step (d) comprising the middle distillate fraction obtained in step (c) and one or more light fractions of step (a) or at least a part of the product thereof. The method for producing a synthetic middle distillate according to any one of claims 40 to 58, wherein the mixture is obtained by mixing the components in a volume ratio of 1: 1 to 9: 1. 60. The product of step (d) comprising the middle distillate fraction obtained in step (c) and one or more light fractions of step (a) or at least a part of the product thereof. The method for producing a synthetic middle distillate according to claim 59, wherein the method is obtained by mixing at a volume ratio of 2: 1 to 6: 1. 61. The product of step (d) comprising the middle distillate fraction obtained in step (c) and one or more light fractions of step (a) or at least a part of the product thereof. And the mixture is mixed at a volume ratio of 84:16 to produce a synthetic intermediate distillate according to any one of claims 58 to 60. 62. A synthetic middle distillate fraction substantially as described and illustrated herein. 63. A diesel fuel composition substantially as described and described herein. 64. A process for producing a synthetic middle distillate having a cetane number greater than 70, substantially as described and illustrated herein. 65. A new process for producing a new synthetic middle distillate fraction, a novel diesel fuel composition, or a synthetic middle distillate having a cetane number greater than 70, substantially as described herein.