CN100593533C - Highly paraffinic, moderately aromatic distillate fuel blend stocks prepared by low pressure hydroprocessing of fischer-tropsch products - Google Patents

Abstract

The invention relates to a distillate fuel comprising a highly paraffinic, moderately aromatic distillate fuel blend stock. The highly paraffinic, moderately aromatic distillate fuel blend stock exhibits excellent combustion properties in diesel and jet engines as a result of the high paraffin content. In addition, the highly paraffinic, moderately aromatic distillate fuel blend stock exhibits improved seal-swell characteristics as a result of the moderate aromatic content. The blend stock is preferably prepared from a Fischer-Tropsch derived product that is hydroprocessed under conditions during which a moderate amount of aromatics are formed.

Description

The high paraffinicity of the low-voltage hydrogenation Processing of Preparation by fischer-tropsch products, the distillate fuel of medium aromaticity content blending oil plant

Related application

The application is the U.S. Patent application No.09/999 of application on October 19 calendar year 2001, and the part of 667 " the distillate fuel tempered oils that the sealing swelling property that is prepared by fischer-tropsch products improves " continues, and its content is incorporated herein for reference.The application also relates to simultaneously being entitled as of the application U.S. Patent application No.10/464 of " the unsaturated distillate fuel blending of the stable moderate oil plant of the low-voltage hydrogenation Processing of Preparation by fischer-tropsch products ", 635 (file number 005950-830).

Invention field

The present invention relates to improved sealing swelling property, comprise the distillate fuel of fischer-tropsch distillate blending of fuel oil plant.

Background of invention

Distillate fuel from Fischer-Tropsch process is high paraffin, has excellent ignition quality and sulphur content extremely low.This makes fischer-tropsch products be fit to very much the of great concern fuel applications of environmental problem.But because of the high characteristic of its paraffinicity, fischer-tropsch distillate fuel has the problem of sealing swelling property difference.

Reduction is known as the aromaticity content of the distillate fuel of diesel oil fuel or jet fuel to diesel oil and the influence of jet engine sealing swollen, and the California becomes particularly important when conventional diesel oil fuel converts low aromatics diesel fuel (LAD) to.The aromaticity content of LAD is non-vanishing, but must be lower than 10%.The reference that relates to the problem that aromaticity content ran into that reduces distillate fuel comprises: Transport Topics, National Newspaper of theTrucking Industry, Alexandria, VA, " Fuel Pump Leaks Tied to Low Sulfur; " October11,1993; Oil Express, and " EPA ' s diesel rules leading to shortages, fleet problems, pricehikes, " October 11,1993, p4; Marin Independent Journal, " Motorists in Marin angryover fuel change, " November 11,1993, p A1; San Jose Mercury News, " Mechanicsfinger new diesel fuel, " December 3,1993; And San Francisco Chronicle, and " ProblemsWith New Diesel Fuel, Clean Air, Angry California Drivers, " December 23,1993

The problem of sealing swelling difference can be monitored by the swelling of measuring gasket.Can utilize known test to monitor the swelling of gasket.For example, a kind of testing method is described in SAE PaperNo.942018, " Effect of Automotive Gas Oil Composition onElastomer Behavior; " among the October 1994, sealing swelling and changes in hardness have wherein been described, be as far as possible based on British Standard (BS) method BS 903 Part A 16[BritishStandard Institute, ' Methods for testing vulcanized rubber, ' Part A 16:1987-Determination of the effect of liquids] test method in measure the testing method of this method and the influence of American Society for Testing andMaterials (ASTM) procedures D471[rubber properties-liquid] with the testing method of D2240[rubber properties-Shore hardness] roughly similar (referring to Figure 12).This paper studies the following elastomeric volume swelling of five classes: hydrogenated nitrile, low nitrile, middle nitrile and low nitrile rubber and fluorocarbon elastomer.

California on March 29th, 1996 gubernatorial " Diesel Fuel Task Force FinalReport " has provided the work summary that the problem of assessing relevant California low-sulfur/low aromatic fuel is carried out.This report mention O shape ring in fuel, soak before and the result that measures afterwards: the testing method of the influence by ASTM D471[rubber properties-liquid] volume and weight measured changes, testing method by ASTMD1415[rubber properties-international hardness] hardness measured, and the testing method by ASTM D1414[RUBBER O shape ring] Young's modulus, ultimate tensile strength and the elongation measured.

Bring sealing swelling problem owing to be transformed into low aromatic fuel from conventional distillate fuel, it is bigger to estimate to be transformed into the sealing swelling problem of being brought by the high paraffin distillate fuel component of Fischer-Tropsch process preparation.Follow the bigger sealing swelling problem of fischer-tropsch distillate fuel element may limit the use of fischer-tropsch distillate fuel.

Another problem that accompanies with high paraffin distillate fuel is the hydrotreatment consumption hydrogen of these fuel.The carrying cost of the production of hydrogen and necessity is very high.Therefore, wish to reduce or eliminate this hydrogen needs.

Thereby this area need seal acceptable distillate fuel of swelling property and distillate fuel blending oil plant.Finally, this area needs and can concoct oil plant by gratifying distillate fuel of the character that fischer-tropsch products obtains and distillate fuel.The invention provides such distillate fuel and blending oil plant and preparation method thereof.

Summary of the invention

The present invention relates to a kind of distillate fuel, comprise fischer-tropsch distillate blending of fuel oil plant.This fischer-tropsch distillate blending of fuel oil plant is included in aromatic hydrocarbons and 80% (weight) or the more paraffin between 2 and 20% (weight).The cetane value index of this fischer-tropsch distillate blending of fuel oil plant is greater than 60, and a ℃ volume change of measuring in following 70 hours is at least 0.25% in 23+/-2 with Buta N nitrile O shape ring by ASTMD471.

In another embodiment, the present invention relates to a kind of fischer-tropsch diesel oil fuel blending oil plant.This fischer-tropsch diesel oil fuel tempered oil material package is contained in aromatic hydrocarbons, 90% (weight) or the more paraffin between 5 and 10% (weight) and is lower than the sulphur of 1ppm.Described aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20% (weight), preferably is lower than the polynuclear aromatic hydrocarbons of 10% (weight).The feature of this fischer-tropsch diesel oil fuel blending oil plant comprises: the cetane value index is greater than 60, press ASTM D6468 reflectivity when down measuring 90 minutes for 150 ℃ surpass 65% and by ASTM D471 a ℃ volume change of measuring in following 70 hours is at least 0.5% in 23+/-2 with Buta N nitrile O shape ring.

In another embodiment, the present invention relates to a kind of fischer-tropsch jet fuel blending oil plant again.This fischer-tropsch jet fuel tempered oil material package is contained in aromatic hydrocarbons, 90% (weight) or the more paraffin between 5 and 10% (weight) and is lower than the sulphur of 1ppm.Described aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20% (weight), preferably is lower than the polynuclear aromatic hydrocarbons of 10% (weight).The feature of this fischer-tropsch jet fuel blending oil plant comprises: smoke point is 30mm or bigger, 260 ℃ of volume change that were tested and appraised and passed through ℃ measurement in following 70 hours in 23+/-2 of ASTM D471 usefulness ButaN nitrile O shape ring in following 2.5 hours are at least 0.5% in ASTM D3241 (JFTOTProcedure).

In another embodiment, the present invention relates to the preparation method of a kind of high paraffinicity, medium aromaticity content distillate fuel blending oil plant again.This method comprises by Fischer-Tropsch process to be made synthetic gas change into Fischer-Tropsch derived feed and described Fischer-Tropsch derived feed is carried out hydrotreatment.Recovery is included in aromatic hydrocarbons and 80% (weight) between 2 and 20% (weight) or the high paraffinicity of more paraffin, medium aromaticity content distillate fuel blending oil plant.Hydroprocessing condition comprises: temperature 525-775 °F, pressure is lower than 1000psig, and liquid hourly space velocity is greater than 0.25hr ^-1

Again in another embodiment, the present invention relates to the preparation method of a kind of high paraffinicity, medium aromaticity content distillate fuel blending oil plant, comprise by Fischer-Tropsch process and make synthetic gas change into Fischer-Tropsch derived feed and described Fischer-Tropsch derived feed is carried out hydrotreatment produce distillate fuel blending oil plant.Add in described distillate fuel blending oil plant that aromatic hydrocarbons blending oil plant produces the aromatic hydrocarbons and 80% (weight) that is included between 2 and 20% (weight) or the high paraffinicity of more paraffin, medium aromaticity content distillate fuel is concocted oil plant.

In another embodiment, the present invention relates to a kind of distillate fuel, comprise fischer-tropsch distillate blending of fuel oil plant.This fischer-tropsch distillate blending of fuel oil plant is to prepare by the method that may further comprise the steps: make synthetic gas change into Fischer-Tropsch derived feed by Fischer-Tropsch process; Be lower than 1000psig and liquid hourly space velocity greater than 0.25hr at temperature 525-775, pressure ^-1Condition under described Fischer-Tropsch derived feed is carried out hydrotreatment; With recovery fischer-tropsch distillate blending of fuel oil plant.The fischer-tropsch distillate blending of fuel oil plant that is reclaimed is included in aromatic hydrocarbons and 80% (weight) or the more paraffin between 2 and 20% (weight).

Again in another embodiment, the present invention relates to a kind of working method of diesel motor, comprise with fischer-tropsch diesel oil fuel blending oil plant and make diesel oil fuel that wherein said fischer-tropsch diesel oil fuel tempered oil material package is contained in aromatic hydrocarbons, 90% (weight) or the more paraffin between 5 and 10% (weight) and is lower than the sulphur of 1ppm.Described aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20% (weight), preferably is lower than the polynuclear aromatic hydrocarbons of 10% (weight).The feature of this fischer-tropsch diesel oil fuel blending oil plant comprises: the cetane value index is greater than 60, press ASTM D6468 reflectivity when down measuring 90 minutes for 150 ℃ surpass 65% and by ASTM D471 a ℃ volume change of measuring in following 70 hours is at least 0.5% in 23+/-2 with Buta N nitrile O shape ring.

Again in another embodiment, the present invention relates to a kind of working method of jet engine, comprise with fischer-tropsch jet fuel blending oil plant and make jet fuel that wherein said fischer-tropsch jet fuel tempered oil material package is contained in aromatic hydrocarbons, 90% (weight) or the more paraffin between 5 and 10% (weight) and is lower than the sulphur of 1ppm.Described aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20% (weight), preferably is lower than the polynuclear aromatic hydrocarbons of 10% (weight).The feature of this fischer-tropsch jet fuel blending oil plant comprises: smoke point is 30mm or bigger, 260 ℃ of volume change that were tested and appraised and passed through ℃ measurement in following 70 hours in 23+/-2 of ASTM D471 usefulness Buta N nitrile O shape ring in following 2.5 hours are at least 0.5% in ASTM D3241 (JFTOT Procedure).

Specifically, the application discloses following invention:

1. a distillate fuel comprises fischer-tropsch distillate blending of fuel oil plant, and wherein said fischer-tropsch distillate blending of fuel oil plant comprises:

A) aromatic hydrocarbons between 2 and 20 weight %; With

B) 80 weight % or more paraffin;

C) greater than 60 cetane value index; With

D) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.25% volume change by ASTM D471 with Buta N nitrile O shape.

2. the fuel of heading 1, nearly 100 weight % of wherein said distillate fuel are fischer-tropsch distillate blending of fuel oil plants.

3. the fuel of heading 1 also comprises oil blending oil plant.

4. the fuel of heading 3, wherein said fuel comprise 5 to 75 weight % fischer-tropsch distillate blending of fuel oil plants and 95 to 25 weight % oil blending oil plant.

5. the fuel of heading 1, at least a portion of wherein said aromatic hydrocarbons come from aromatic hydrocarbons blending oil plant.

6. the fuel of heading 1, wherein said fischer-tropsch distillate blending of fuel oil plant is included in the aromatic hydrocarbons between the 2 and 15 weight %.

7. the fuel of heading 1, wherein said fischer-tropsch distillate blending of fuel oil plant is included in the aromatic hydrocarbons between the 5 and 10 weight %.

8. the fuel of heading 1, wherein said fischer-tropsch distillate blending of fuel oil plant comprise at least 0.5% the volume change of measuring by ASTM D471.

9. the fuel of heading 1, wherein said fischer-tropsch distillate blending of fuel oil plant comprise at least 2% the volume change of measuring by ASTM D471.

10. the fuel of heading 1, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is less than 20 weight %.

11. the fuel of heading 1, wherein said distillate fuel also comprises the sulphur that is lower than 1ppm.

12. the fuel of heading 1, wherein said distillate fuel also comprises the nitrogen that is lower than 1ppm.

13. the fuel of heading 1, wherein said distillate fuel also comprises antioxidant.

14. the fuel of heading 1, wherein said distillate fuel meet at least one technical requirements of diesel oil or jet fuel.

15. the fuel of heading 14, wherein said distillate fuel meet at least one technical requirements of diesel oil fuel, and the cetane value index is greater than 65.

16. pressing ASTM D6468 reflectivity when measuring 90 minutes down for 150 ℃, the fuel of heading 15, wherein said fuel surpasses 65%.

17. the fuel of heading 14, wherein said distillate fuel meet at least one technical requirements of jet fuel, 260 ℃ were tested and appraised in following 2.5 hours in ASTM D3241.

18. a fischer-tropsch diesel oil fuel blending oil plant comprises:

A) aromatic hydrocarbons between 5 and 10 weight %, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20 weight %;

B) 90 weight % or more paraffin;

C) be lower than the sulphur of 1ppm;

D) greater than 60 cetane value index;

E) press ASTM D6468 when measuring 90 minutes down for 150 ℃, surpass 65% reflectivity; With

F) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.5% volume change by ASTM D471 with Buta N nitrile O shape.

19. the blending oil plant of heading 18, the cetane value index of wherein said blending oil plant is greater than 65.

20. the blending oil plant of heading 18, the cetane value index of wherein said blending oil plant is greater than 70.

21. the blending oil plant of heading 18, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 10 weight %.

22. a fischer-tropsch jet fuel blending oil plant comprises:

A) aromatic hydrocarbons between 5 and 10 weight %, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20 weight %;

B) 90 weight % or more paraffin;

C) be lower than the sulphur of 1ppm;

D) 30mm or bigger smoke point;

E) in ASTM D3241 260 ℃ be tested and appraised in following 2.5 hours; With

F) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.5% volume change by ASTM D471 with Buta N nitrile O shape.

23. the blending oil plant of heading 22, wherein said blending oil plant in ASTM D3241 270 ℃ be tested and appraised in following 2.5 hours.

24. the blending oil plant of heading 22, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 10 weight %.

25. the working method of a diesel motor comprises with the fischer-tropsch blending oil plant of heading 18 and makes diesel oil fuel.

26. the diesel motor working method of heading 25, wherein said diesel oil fuel also comprise oil blending oil plant.

27. the diesel motor working method of heading 25, wherein said diesel oil fuel also comprises antioxidant.

28. the working method of a jet engine comprises with the fischer-tropsch blending oil plant of heading 22 and makes jet fuel.

29. the jet engine working method of heading 28, wherein said jet fuel also comprise oil blending oil plant.

The accompanying drawing summary

Fig. 1 is the block diagram of one embodiment of this invention.

Fig. 2 is the diagram that concerns between the volume change of concoction of the blending oil plant of high paraffinicity distillate fuel described in the embodiment and alkylaromatic hydrocarbon or alkyl naphthene and the cetane value index.

Detailed Description Of The Invention

According to the present invention, found that high paraffin content, medium arene content distillate fuel blending oil plant have improved sealing swellability. This distillate fuel blending oil plant can be by comprising that Fischer-Tropsch is synthetic and forming the method preparation of hydrotreatment under the condition of medium arene content. This high paraffin content, medium arene content distillate fuel blending oil plant can be concocted oil plant with other and mix distillate fuel is provided, and perhaps can only have there not being other to concoct oil plant in the situation of a small amount of additive of optional adding directly to make fuel in engine.

For the present invention, adopt herein to give a definition:

Term " aromatic hydrocarbons " means to comprise the ring plain unsaturated hydrocarbons of the uninterrupted electron cloud of odd number B duplet.

" distillate fuel blending oil plant " is to mix with other distillate fuel blending oil plant to provide the particularly material of diesel oil or jet fuel of distillate fuel, as defined herein. This blending oil plant itself needn't satisfy the specification requirement of each fuel, but the composition of preferred gained blending oil plant meets the demands. Jet fuel blending oil plant and other jet fuel blending oil plant and optional additive combination provide jet fuel. Similarly, diesel fuel blending oil plant and other diesel fuel blending oil plant and optional additive combination provide diesel fuel.

" aromatic hydrocarbons blending oil plant " is to comprise more than or equal to 50% (weight), preferably greater than or equal to 75% (weight), most preferably more than or equal to the blending oil plant of 90% (weight) aromatic hydrocarbons. If make aromatic hydrocarbons blending oil plant with pure aromatic product, then needn't analyze arene content. If aromatic hydrocarbons blending oil plant comprises aromatic hydrocarbons and other hydrocarbon, then the ASTM D6550 of available modification (measuring the standard method of test of the olefin(e) centent of gasoline by supercritical fluid chromatography (SFC)) measures aromatic hydrocarbons. Aromatic hydrocarbons blending oil plant can concoct to improve with fischer-tropsch distillate blending of fuel oil plant the arene content of fischer-tropsch distillate blending of fuel oil plant. The example of aromatic hydrocarbons blending oil plant comprises the pure aromatics (such as benzene and alkylbenzene etc.) that is purchased; The aromatic hydrocarbons that is obtained by the conventional oil product; With the reformable fischer-tropsch products aromatic hydrocarbons that obtains etc. of reforming.

ASTM D471 is contained the required method of contrast ability that rubber and rubber-like composition stand liquid of estimating. Be designed for vulcanized rubber sample, the sample that from the fabric that scribbles vulcanized rubber, cuts out or finished market product that test cuts out from standard plate. ASTM D471 has stipulated that under the temperature and time condition of determining sample is subject to the method for operating of liquid. By measure in test(ing) liquid, soak before and the afterwards variation of quality, volume and size determine to produce rotten. This test is used in particular for some rubber, for example may contact sealing gasket, packing ring, flexible pipe, barrier film and the sleeve pipe of oil, grease, fuel and other liquid in the use procedure. Those skilled in the art are easy to measure with ASTM D471 the change in volume evaluation distillate fuel of sealing gasket or packing ring. It is to be understood that although fuel of the present invention demonstrates the change in volume of measuring by ASTM D471, but what in fact demonstrate change in volume is rubber or rubber-like composition and on-fuel itself.

Buna N O shape ring is the sealing gasket that is applicable to ASTM D471 of being made by the nitrile elastomer. Other nitrile O shape ring that is applicable to ASTM D471 can be by many sources such as American United (compound C-70) and Parker Seals acquisition. Parker Seals provides three class O shapes ring: standard nitrile, N674 type; The nitrile of anti-fuel (high acrylic acid acrylonitrile), the N497 type; And fluorocarbons, the V747 type. Wherein, standard nitrile O shape ring is unique ASTM D471 that is applicable to, because it is similar to O shape ring commonly used in the present Diesel engine. Encircling with fluorocarbons O shape of anti-fuel is not the packing ring of typical broad commercial applications.

The Cetane number index is to measure for the standard method of test of the Cetane number index that is calculated by four variable equatioies by ASTM D4737-96a (2001).

The conventional oil product comprises by crude oil derived product.

" oil blending oil plant " is the blending oil plant that comprises the conventional oil product. The overhead gas stream that oil blending oil plant can be obtained by crude oil or refined product distillation and form as the residual fuel of non-volatile remainder.

Meaning described raw material, blending oil plant or product from Fischer-Tropsch process comes from Fischer-Tropsch process or produces in certain stage by Fischer-Tropsch process.

" fischer-tropsch distillate blending of fuel oil plant " is the blending oil plant that comes from Fischer-Tropsch process or produce in certain stage by Fischer-Tropsch process. Fischer-tropsch distillate blending of fuel oil plant can mix with other distillate fuel blending oil plant provides distillate fuel, particularly diesel oil or jet fuel. This blending oil plant itself needn't satisfy the specification requirement of each fuel, but the composition of gained blending oil plant meets the demands. Fischer-tropsch distillate blending of fuel oil plant comprises Fischer-Tropsch diesel fuel blending oil plant and Fischer-Tropsch jet fuel blending oil plant. As mentioned above, fischer-tropsch distillate blending of fuel oil plant can be concocted oil plant with other and mix distillate fuel is provided, and perhaps fischer-tropsch distillate blending of fuel oil plant can only have there not being other blending oil plant in the situation of a small amount of additive of optional adding directly make fuel in engine.

Distillate fuel is the material that contains the hydrocarbon of boiling point between about 60 to 1100 °F. Comprise that the concrete fuel of naphtha, jet fuel, diesel fuel, kerosene, aviation gasoline, fuel oil and tempered oil thereof is in the large class of distillate fuel.

Diesel fuel is the material that is applicable to Diesel engine. Preferred diesel fuel meets following specification requirement one of at least:

ASTM D975-" standard-required of diesel fuel oil "

Europe grade CEN 90

Japan fuel standard JIS K 2204

U.S. weights and measures meeting (NCWM) 1997 is about the index of senior diesel fuel

The index (FQP-1A) of the senior diesel fuel that U.S. engine building association is recommended

Diesel fuel can or not have other blending oil plant and only is comprised of the single blending oil plant of a small amount of additive of optional adding by the composition of blending oil plant.

Jet fuel is to be adapted at the material that uses in the turbogenerator of aviation or other purposes. Preferred jet fuel meets following specification requirement one of at least:

·ASTM D1655，

·DEF STAN 91-91/3(DERD 2494)，TURBINE FUEL，AVIATION，

·KEROSENE TYPE，JET A-1，NATO CODE：F-35，

·International Air Transportation Association(IATA)Guidance Materials for Aviation，4th edition，March 2000

Jet fuel can or not have other blending oil plant and only is comprised of the single blending oil plant of a small amount of additive of optional adding by the composition of blending oil plant.

Fischer-Tropsch diesel fuel blending oil plant is the blending oil plant that is applicable to Diesel engine. This Fei-Tuo diesel fuel blending oil plant can be concocted oil plant with other and mix diesel fuel is provided, and perhaps can only have there not being other to concoct oil plant in the situation of a small amount of additive of optional adding to use.

The Fischer-Tropsch jet fuel is to be adapted at the blending oil plant that uses in the turbogenerator of aviation or other purposes. Fischer-Tropsch jet fuel blending oil plant can be concocted oil plant with other and mix jet fuel is provided, and perhaps can only have there not being other to concoct oil plant in the situation of a small amount of additive of optional adding to use.

High paraffin content, medium arene content distillate fuel blending oil plant be contain more than 70% (weight) paraffin, preferred 80% (weight) or more paraffin, most preferably 90% (weight) or more paraffin and 2 to 20% (weight) aromatic hydrocarbons, preferred 2 to 15% (weight) aromatic hydrocarbons, most preferably the distillate fuel of 5 to 10% (weight) aromatic hydrocarbons is concocted oil plant. Preferred this high paraffin content, medium arene content distillate fuel blending oil plant are fischer-tropsch distillate blending of fuel oil plants.

" Fischer-Tropsch derived feed " or " Fischer-Tropsch raw material " is the raw material that comes from Fischer-Tropsch process or produce in certain stage by Fischer-Tropsch process. In the inventive method, Fischer-Tropsch derived feed can be concocted the oil plant blending with oil the blending logistics is provided in technical process.

Reformable fischer-tropsch products is the product from the reformable one-tenth aromatic hydrocarbons of Fischer-Tropsch process. Usually in about boiling below 400 °F, preferred reformable light fraction contains the hydrocarbon that boiling point is higher than pentane and is lower than 400 °F in reformable light fraction. More preferably the boiling range of reformable light fraction is such so that reforms the rear mononuclear aromatics that boiling point is higher than pentane (97 ℃) and is lower than n-decane (346 ℃) that produces. Most preferably described boiling range is to produce benzene as reformate after so consequently reformation, and the boiling range of reformable fischer-tropsch products is higher than n-hexane and is lower than n-decane.

Synthesis gas is the mixture that comprises hydrogen and carbon monoxide. Except these materials, may also there be water, carbon dioxide, unconverted light hydrocarbon feedstocks and various impurity.

The arene content of the high paraffin content of the present invention, medium arene content blending oil plant is between 2 and 20% (weight), preferably between 2 and 15% (weight), most preferably between 5 and 10% (weight). This arene content improves the sealing swellability of measuring by ASTM D1414. The method of testing of ASTM D1414 comprises the test with ℃ measurement volumes variation in lower 70 hours in 23+/-2 of Buta N nitrile O shape ring by ASTM D471. This volume change surpasses 0.25%, preferably surpasses 0.5%, most preferably surpasses 2%. The aromatic hydrocarbons that the present invention concocts oil plant mainly is monokaryon aromatic hydrocarbons (alkylbenzene), and a small amount of polynuclear aromatic hydrocarbons is arranged. Preferred described aromatic hydrocarbons comprise be less than 25% (weight) polynuclear aromatic hydrocarbons, more preferably less than 20% (weight) polynuclear aromatic hydrocarbons, most preferably be less than 10% (weight) polynuclear aromatic hydrocarbons.

The ASTM D6550 of modification (measuring the standard method of test of the olefin(e) centent of gasoline by supercritical fluid chromatography (SFC)) is used for measuring the type of raw material and product. This process variant adopts the total amount of 3 point calibration standard saturated hydrocarbons, aromatic hydrocarbons, oxygenatedchemicals (polarity) and alkene. Calibration solution prepares with following compound: hendecane, toluene, n-octyl alcohol and dodecylene. Quantize with external standard method, detecting of aromatic hydrocarbons and oxygenatedchemicals is limited to 0.1% (weight), and detecting of alkene is limited to 1.0% (weight). ASTM D6550 describes instrument condition.

Aliquot is seldom injected two chromatographic columns of one group of series connection, move as mobile phase with supercritical carbon dioxide. The first column filling high surface silicon oxide particle. The second post is equipped with the high surface silicon oxide particle of load silver ion.

Guide inhomogeneous component to arrive detector through chromatographic system with double block valve. With concurrent, saturated hydrocarbons (just with branched paraffin and cycloalkane) arrives detector through two posts, and alkene is trapped within on the post that carries silver, and aromatic hydrocarbons and oxygenatedchemicals are stayed on the silicon oxide column. With backwash mode aromatic and oxygenatedchemicals are eluted to the detector from silicon oxide column subsequently. At last, with alkene from carry silver-colored post backwash to detector.

(FID) quantizes with flame ionization detector. Based on the area calibration with respect to the chromatographic signal of standard reference material of saturated hydrocarbons, aromatic hydrocarbons, oxygenatedchemicals and alkene, the standard reference material contains total saturated hydrocarbons, aromatic hydrocarbons, oxygenatedchemicals and the alkene of the known quality % of density correction. The gross mass of collecting is 100%+/-3%, for conveniently being normalized to 100%.

The polynuclear aromatic hydrocarbons of product (PNA) content is measured diesel fuel and the arene content of aviation turbine fuel and the standard test method of polynuclear aromatic hydrocarbons content by ASTM D5186-99 by supercritical fluid chromatography and is measured.

Utilize following algorithm by the paraffin content of supercritical fluid chromatography (SFC) Analysis deterrmination product. SFC analyzes the measurement result that aromatic hydrocarbons, alkene, oxygenatedchemicals and saturated hydrocarbons are provided. Saturated hydrocarbons during this analyzes is the set of alkane and naphthene (being cycloalkane). Therefore,

Alkane=saturated hydrocarbons (SFC)-naphthene

But do not find that naphthene is present in the product of the present invention with relatively large (be lower than saturated hydrocarbons 10%). Therefore, the saturated hydrocarbons of analyzing from SFC can be considered the suitable tolerance of the paraffin content of product of the present invention usually.

For confirming not exist relatively large naphthene, measure independently the content of cycloalkane with GC-MS. The total amount of GC-MS report alkene and cycloalkane, because identical hydrogen/carbon ratio is arranged in its structure, this technology can not be distinguished. If the total amount of GC-MS report alkene and cycloalkane is less, then only there is a small amount of naphthene in deducibility. If but GC-MS reports that this total amount is larger, then can from the GC-MS total amount, deduct the amount that olefin(e) centent (measuring by SFC) is determined the naphthene part.

Naphthene=(naphthene of measuring by GC-MS and the total amount of alkene)-(alkene of measuring by SFC)

Then can from saturated hydrocarbon content (measuring by SFC), deduct the suitable measurement result that naphthene obtains paraffin content by the first equation. If the naphthene content of determining like this, then is recorded as zero less than zero, and in calculating paraffin content, use zero. Alkane equals the SFC saturated hydrocarbons like this, in the case.

In the GC-MS test, determine the amount of alkane, alkene, pure and mild acid with deuterium-labelled standard sample. Selected deuterium-labeled compound is added in the tested sample as interior mark. Mixture with trimethyl silyl (TMS) agent treatment sample and standard sample forms the TMS derivative, then carries out GCMS and analyzes. Mass spectrograph on the Hewlett-Packard platform that mass spectrograph is with the HP GC that 60 meters non-polar columns are arranged engages. Normal paraffin hydrocarbons and branched paraffin all use deuterium-labelled normal paraffin hydrocarbons to quantize. Alkene, pure and mild acid all use corresponding deuterium-labeled compound to quantize.

The paraffin content of the blending oil plant of the high paraffin content of the present invention, medium arene content is at least 70% (weight), preferred 80% (weight) or higher, 90% (weight) or higher most preferably. Because its paraffin content is high, the high paraffin content of the present invention, medium arene content distillate fuel blending oil plant have excellent flammability. The peculiar flammability that the present invention concocts oil plant comprises that smoke point surpasses 25mm, preferably surpasses 30mm, and the Cetane number index surpasses 60, preferably surpasses 65. This paraffin by just with the compositions of mixtures of different-alkane, the ratio of different/normal paraffin hydrocarbons is between 0.3 and 10. When this blending oil plant plans to use in cold weather (Jet Al or the diesel oil that uses the arctic), the isoparaffin ratio is higher to be preferred.

The fuel that comprises the high paraffin content of the present invention, medium arene content blending oil plant preferably meets at least one specification requirement of diesel oil or jet fuel. This fuel can or not have other blending oil plant and only is comprised of the described high paraffin content of a small amount of additive of optional adding, medium arene content blending oil plant by the composition of blending oil plant. Described high paraffin content, medium arene content are concocted oil plant and are comprised this fuel quantity ga(u)ge of concocting oil plant and reveal acceptable at least (in most cases fabulous) stability. The reflectivity of the diesel fuel that comprises described high paraffin content, medium arene content blending oil plant of for example, measuring by ASTM D6468 under 150 ℃ surpasses 65% (when measuring 90 minutes). The jet fuel that comprises described high paraffin content, medium arene content blending oil plant in ASTM D3241 (JFTOT Procedure) 260 ℃ be tested and appraised in lower 2.5 hours. Be tested and appraised corresponding to the tubular type rating less than 3 (Code 3), cross over the pressure drop of filter less than 25mmHg.

The fuel that the present invention concocts oil plant and comprises this blending oil plant usually have low-sulfur (＜1ppm) and preferred low nitrogen content (＜1ppm). Thereby the hetero atom oxide that discharges in the environment reduces. Therefore, this blending oil plant is eco-friendly with the fuel that comprises this blending oil plant.

Fischer-Tropsch process

The present invention concocts oil plant and can be prepared by fischer-tropsch products, carries out hydrotreatment under the condition that forms moderate aromatic hydrocarbons. Preferred the present invention concocts that oil plant is at least part of to be prepared by fischer-tropsch products.

In the Fischer-Tropsch chemistry, make synthesis gas change into liquid hydrocarbon by under reaction condition, contacting with Fischer-Tropsch catalyst. Typically, methane can be sent into conventional synthetic gas generator with optional heavier hydrocarbon (ethane and heavier) synthesis gas is provided. Synthesis gas generally contains hydrogen and carbon monoxide, can comprise a small amount of carbon dioxide and/or water. It is undesirable having sulphur, nitrogen, halogen, selenium, phosphorus and arsenic impurities in the synthesis gas. For this reason, according to the quality of synthesis gas, preferably before carrying out Fei-Tuo chemistry, from raw material, remove desulfuration and other pollutant. The method that removes these pollutants is as well known to those skilled in the art. For example, preferably remove sulphur impurity with ZnO protection bed. The method that removes other pollutant is as well known to those skilled in the art. May also wish any other sulphur compound of before the Fischer-Tropsch reaction device, making the synthesis gas purifying remove the carbon dioxide that produces in the synthesis gas reaction process and not yet remove. This can contact realization with weakly alkaline solution (for example wet chemical) by for example making synthesis gas in packed column.

In Fischer-Tropsch process, comprise H₂Under the temperature and pressure reaction condition that is fit to, contact the liquid gentle attitude hydrocarbon of generation with the synthesis gas of CO mixture with Fischer-Tropsch catalyst. Fischer-Tropsch reaction generally can be carried out under the following conditions: temperature about 300 to 700 °F (149-371 ℃), preferred about 400 to 550 °F (204-228 ℃); About 10 to 600psia (0.7-41bar) of pressure, preferred 30 to 300psia (2-21bar); With catalyst air speed about 100 to about 10000cc/g/hr, preferred 300 to 3000cc/g/hr.

Fischer-Tropsch process can be divided into high temperature Fischer-Tropsch process or low temperature Fischer-Tropsch process. The process conditions of two kinds of methods are different with major product.

The high temperature Fischer-Tropsch process generally be higher than 250 ℃, preferably or be higher than 350 ℃ temperature and carry out. The high temperature Fischer-Tropsch process mainly obtains generally at C₃To C₈Lower molecular weight olefin product in the scope, preferred propylene is to amylene. The high temperature fischer-tropsch products may also contain a large amount of aromatic hydrocarbons. The high temperature fischer-tropsch products can make aromatic saturation through processing, and comprising reforms processes. Olefin product from the high temperature Fischer-Tropsch process is further processed to produce highly branched iso-paraffinic products through oligomeric and step of hydrogenation usually. Can treatedly make it to satisfy the specification requirement of gasoline from the product of high temperature Fischer-Tropsch process. From usually have an appointment 55 Cetane number index of the product of high temperature Fischer-Tropsch process, because this product is highly branched. One example of high temperature Fischer-Tropsch process is the Synthol method that SASOL adopts, as " High Yield High Quality Diesel from Fischer Tropsch Process, Dry, M.E., Chem.S.A. is described in the February 1984.

Jet fuel is also by high temperature Fischer-Tropsch process, olefin oligomerization and hydrogenation production.The high temperature Fischer-Tropsch process that is used to prepare jet fuel is described in that " Qualification ofSASOL Semi-Synthetic Jet A-1 as Commercial Jet Fuel, " SwRI-8531 is among the November 1997.Described in this reference, by the jet fuel aromatic free or the unsaturated hydrocarbons of high temperature Fischer-Tropsch process preparation.Thermostability (or JFTOT) weight break point of tempered oil that provides fischer-tropsch derived jet fuel of high temperature and conventional oil derivatived fuel in the document is above 300 ℃.Thereby the thermostability of this semi-synthetic tempered oil (or JFTOT) weight break point is apparently higher than 260 ℃ technical requirements.Referring to " Qualification of SASOLSemi-synthetic Jet A-1 as Commercial Jet Fuel ", Moses, Stavinoha, and Roets, South West Research Institute PublicationSwRI-8531, November 1997.

The researchist of the tempered oil of researching high-temperature fischer-tropsch products and high temperature fischer-tropsch products and petroleum derivation product is the stability of attention problem not.

The low temperature Fischer-Tropsch process is operated being lower than under 250 ℃ the temperature, produces heavier product.The heavier product of low temperature Fischer-Tropsch process mainly comprises wax usually.Product from the low temperature Fischer-Tropsch process has made it acceptable peroxide stability through hydrotreatment usually, as US6, shown in 180,842.Therefore, make with extra care as hydrogen treatment and hydrocracking through the hydrotreatment operation usually from the product of low temperature Fischer-Tropsch process the steady fuel that satisfies technical requirements is provided.Product from the low temperature Fischer-Tropsch process mainly is a straight chain, even after hydrocracking, and these products also contain recently the product side chain still less from the high temperature Fischer-Tropsch process.Less these products that make of side chain have recently the higher cetane value index of product of higly branched chain that has from the high temperature Fischer-Tropsch process in the low temperature Fischer-Tropsch process product.The low temperature fischer-tropsch products has greater than 60 usually, be preferably greater than 70 cetane value index.

The Fischer-Tropsch process that is used to prepare distillate fuel blending oil plant of the present invention is the low temperature Fischer-Tropsch process.The example that carries out the condition of low temperature fischer-tropsch type reaction is as well known to those skilled in the art.

This product can be at C ₁To C ₂₀₀₊Scope in, great majority at C ₅-C ₁₀₀₊Scope in.This reaction can be carried out in various type of reactor for example have the combination of fixed-bed reactor, slurry-phase reactor, fluidized-bed reactor or dissimilar reactors of one or more catalyst bed.This reaction process and reactor are known, and be open in the literature.Slurry Fischer-Tropsch process (being to implement the preferred method of the present invention) utilizes excellent heat transfer (and mass transfer) characteristic to carry out strong exothermic reaction, can produce the paraffins of higher molecular weight when using cobalt catalyst.In a kind of slurry process, comprise H ₂Make progress bubbling by the slurries in the reactor with the synthetic gas of CO mixture as third phase, and these slurries comprise and disperse and be suspended in the granular fischer-tropsch type hydrocarbon synthesis catalyst that is included in reaction conditions under in the slurries of the hydrocarbon product of the building-up reactions of liquid state.The mol ratio of hydrogen and carbon monoxide can be in about wide region of 0.5 to 4, but more typically in about 0.7 to 2.75, preferred about scope of 0.7 to 2.5.

The Fischer-Tropsch catalyst that is fit to comprises one or more group VIII catalytic metal such as Fe, Ni, Co, Ru and Re.In addition, the catalyzer of Shi Heing can contain promotor.Therefore, preferred Fischer-Tropsch catalyst comprises one or more of the cobalt that is supported on the significant quantity on the suitable inorganic carrier material and Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and La, and preferred solid support material comprises one or more refractory metal oxide compound.The amount of cobalt is generally between about 1 and about 50% (weight) of total catalyst composition in the catalyzer.This catalyzer can also contain basic oxide promotor such as ThO ₂, La ₂O ₃, MgO and TiO ₂, promotor such as ZrO ₂, precious metal (Pt, Pd, Ru, Rh, Os, Ir), coinage metal (Cu, Ag, Au) and other transition metal (as Fe, Mn, Ni and Re).Can use the solid support material that comprises aluminum oxide, silicon oxide, magnesium oxide and titanium oxide and composition thereof.The carrier that is preferred for cobalt-containing catalyst comprises titanium oxide.The catalyzer and the preparation thereof that are suitable for are known, and exemplary and nonrestrictive example is US4 for example as seen, 568,663.

Known some catalyzer provides and is low to moderate medium chainpropagation probability, and reaction product comprises the lower molecular weight (C of higher proportion _2-8) high molecular (C of alkene and low ratio ₃₀₊) wax.Known other catalyzer provide higher chainpropagation probability, and reaction product comprises the lower molecular weight (C of low ratio _2-8) high molecular (C of alkene and higher proportion ₃₀₊) wax.This type of catalyzer is as well known to those skilled in the art, is easy to obtain and/or preparation.

Product from the low temperature Fischer-Tropsch reaction generally comprises light reaction product and wax shape reaction product.Wax shape reaction product (being wax slop) comprises that boiling point is higher than about 600 hydrocarbon (for example vacuum gas oil is to heavy paraffin), mainly at C ₂₀₊In the scope, with decrement to C ₁₀Described light reaction product and wax shape product all are that alkane belongs to basically.Wax shape product generally comprises more than 70% (weight) n-paraffin, common 80% (weight) or more n-paraffin.

Oxygenation is handled

Hydrotreatment is generally as well known to those skilled in the art, comprises the methods such as combination such as hydrogen treatment, hydrocracking, hydrogenation, catalytic dewaxing or these methods.Hydrotreatment of the present invention operation is preferably at one or several reactor, most preferably finish several purposes in a reactor.The purpose of hydrotreatment of the present invention is to reduce, preferably remove fully heteroatoms such as nitrogen and sulphur.Further, described hydrotreatment can reduce or remove alkene fully.In addition, described hydrotreatment can improve the ratio that distillates different in the product/n-paraffin.In addition, described hydrotreatment can improve the productive rate that distillates product by transforming heavy substance.At last, different with conventional hydrotreatment, hydrotreatment of the present invention produces the aromatic hydrocarbons of moderate.

Under the condition that produces aromatic hydrocarbons, carry out the clean consumption that hydrotreatment can reduce or eliminate hydrogen in the hydrotreatment process.Must add hydrogen though begin described hydrotreatment process, if the aromatic hydrocarbons growing amount is enough high, the amounts of hydrogen that produces in this process may surpass the initial amounts of hydrogen that adds.Therefore, the present invention has clean hydrogen generation in the hydrogen processing in addition, and promptly clean hydrogen consumption is less than zero.

The hydrogen that produces can be used for various uses in Gas-To-Liquid (GTL) equipment.These are as comprising that the hydrogen treatment of fischer-tropsch logistics is to reduce or eliminate alkene and/or heteroatoms.In addition, the hydrogen of generation can with the GTL process in produce or from containing CO ₂The CO that gas source reclaims ₂Reaction makes CO ₂Reduction.From CO ₂-H ₂The product of reaction can be CO or fischer-tropsch products, and this reaction can be carried out in synthetic gas generator.The hydrogen that produces also can be used for producing fuel as not forming CO ₂The fuel element of discharging.The fuel of being produced can be used for producing Process heat, produces electric energy and/or distillation/purified water.

The representative temperature that fischer-tropsch products is carried out in the hydrotreatment generation aromatic hydrocarbons is 525-775 °F, preferred 575-725 °F.The typical pressure that is used for this operation be lower than 1000psig, preferably be lower than 600psig, most preferably 200 and 500psig between.The typical liquid hourly space velocity (LHSV) that is used for this operation is greater than 0.25hr ^-1, preferably 0.5 and 1.5hr ^-1Between.The typical hydrotreating catalyst that is used for this operation comprises catalyzer (back description) that is used for the hydrotreatment operation or the catalyzer that is used for the hydroisomerization dewaxing, the preferred combination that is used for the catalyzer of hydrotreatment and hydroisomerization dewaxing, because this combination expense is lower, also can reduce the pour point of product simultaneously.

The hydrotreating catalyst of available routine produces aromatic hydrocarbons.The hydrotreating catalyst that is particularly suitable for producing aromatic hydrocarbons is a dual functional catalyst, not only comprises hydrogenation functional group but also comprise acidic functionality.The hydrotreating catalyst that forms aromatic hydrocarbons is to exist acidic functionality with for example difference of conventional hydrogen treatment catalyzer, because the hydrogen treatment catalyzer generally includes nonacid carrier such as aluminum oxide.

Acidic functionality is preferably based on the mixture of at least two kinds of valent metal oxides of difference.Preferred metal oxide mixture comprises SiO ₂And Al ₂O ₃Or Al ₂O ₃, SiO ₂And P ₂O ₅This metal oxide mixture can prepare by this way so that at least a portion metal oxide high dispersing between it, for example SiO ₂And Al ₂O ₃Disperse but not SiO with the atom scale ₂And Al ₂O ₃Phase-splitting.Can check by XRD and determine SiO ₂And Al ₂O ₃The existence of phase-splitting.If all oxides all exists with the phase-splitting form, the performance of this catalyzer will weaken.The example of the acidic functionality of being made up of mixed metal oxide is the SiO of zeolite, crystallization SAPO ' s and co-precipitation ₂-Al ₂O ₃

On the contrary, make petroleum naphtha change into light aromatic hydrocarbons (C ₆-C ₁₀) routine reformation technology use halogen (the most frequently used is chlorine) as acidic functionality usually.Though halogen can be used as acidic functionality in hydrotreating catalyst, the fluorine of fluorided alumina form especially, halogen is not preferred, thereby because they will be lentamente from catalyzer stripping may cause the reaction vessel corrosion.

Hydrogenation functional group in the hydrotreating catalyst of formation aromatic hydrocarbons comprises metal.The metal hydride that is fit to comprises VI family metal such as Mo and/or W and group VIII metal such as Ni or Co.These metals are present on the catalyzer with sulfur form.Preferred metal hydride is a precious metal, more preferably is selected from Pt, Pd and composition thereof.These metals can be sulfurized, but preferably use with the unvulcanised form.

The catalyzer that is applicable to the hydrotreatment operation is known in this field.The catalyzer that is fit to comprises VIIIA family (according to 1975 rules of International Union of Pure and Applied Chemistry) precious metal, for example be supported on platinum or palladium on aluminum oxide or the siliceous matrix, and VIIIA family and group vib, for example be supported on nickel=molybdenum, cobalt-molybdenum, nickel-tungsten or nickel-Xi on aluminum oxide or the siliceous matrix.Base metal (as nickel-molybdenum) metal hydride usually with oxide compound or more preferably or may with sulphided form (when as described in metal when easily forming this compounds) be present in the final catalyst composition.Preferred non-noble metal catalyst compositions contains and surpasses about 5% (weight), preferred about 5 molybdenum and/or tungsten to about 40% (weight) reach at least about 0.5% (weight), preferred about 1 nickel and/or cobalt to about 15% (weight), measures by corresponding oxide.Precious metal (as platinum) catalyzer can contain and surpass 0.01% metal, the preferred metal between 0.1 and 1.0%.Also can use the precious metal combination, for example the mixture of platinum and palladium.

It is more active that matrix component includes acidic catalyst.Activated matrix component comprises the amorphous silica-alumina, perhaps can be zeolite or non-zeolitic crystalline molecular sieve.The example of the substrate molecule sieve that is fit to comprises Y zeolite, X zeolite and so-called overstable Y zeolite and the high Y zeolite of structure silica alumina ratio.The body material that is fit to also can comprise synthetic or crude substance and inorganic materials such as clay, silicon oxide and/or metal oxide such as silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide and ternary composition such as silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silicon oxide-magnesium oxide-zirconium white.The latter can be natural existence or gelatinous precipitate or comprise silicon oxide and the gel form of metal oxide mixture.Can comprise montmorillonite and kaolin group with catalyzer compound naturally occurring clay.These clays can virgin state such as form use original exploitation or that pass through dealuminzation, acid treatment or chemical modification at first.Can use in this reactor more than a class catalyzer.

As mentioned above, hydrotreatment is generally as well known to those skilled in the art, comprises the methods such as combination such as hydrogen treatment, hydrocracking, hydrogenation, catalytic dewaxing or these methods.Hydrotreatment of the present invention is by being selected from the quality that following operation improves Fischer-Tropsch derived feed: the content that reduces sulphur, nitrogen and oxygen in the raw material; Reduce the content of alkene in the raw material; The ratio of different in the product/n-paraffin is risen between 0.3 and 10; By transforming the productive rate of the heavy substance raising distillate fuel in the raw material; And combination.

Typical hydrogen treatment condition changes in wide region.The typical pressure that is used for this operation be lower than 1000psig, preferably be lower than 600psig, most preferably 200 and 500psig between.The typical liquid hourly space velocity (LHSV) that is used for this operation is greater than 0.25hr ^-1, preferably 0.5 and 2.0hr ^-1Between.Hydrogen recycle speed be typically greater than 50 standard cubic feet per barrel oil (SCF/Bb1), preferably 1000 and 5000SCF/Bb1 between.Temperature about 300 to about 750 scope, preferably in 450 to 600 scope.

Hydrocracking can be undertaken by ordinary method well known by persons skilled in the art.Typically, hydrocracking is to make bigger carbon molecule be cracked into process than small molecules.Can contact realization with hydrogen under the following conditions in the presence of the hydrocracking catalyst that is fit to by the combination that makes specific cut or cut: temperature is in the scope of about 600 to 900 (316-482 ℃), preferred 650 to 850 (343-454 ℃), pressure is about 0.1 to 10hr based on the air speed of hydrocarbon feed in the scope of about 200 to 4000psia (13-272atm), preferred 500 to 3000psia (34-204atm) ^-1, preferred 0.25 to 5hr ^-1Hydrocracking generally be used to reduce hydrocarbon molecule size, make the hydrogenation of alkene key, make aromatic hydrocarbons hydrogenation and remove the heteroatoms of trace.The catalyzer that is applicable to the hydrocracking operation is known in the art, and comprises sulphurized catalyst.Sulfide catalyst can comprise amorphous silica-alumina, aluminum oxide, tungsten and nickel.

The hydrogenant condition is industrial known, comprises that temperature is higher than envrionment temperature and pressure greater than normal pressure.Being used for the hydrogenant optimum condition comprises: temperature is between 300 and 800 °F, most preferably between 400 and 600 °F, pressure 50 and 2000psig between, most preferably 100 and 500psig between; Liquid hourly space velocity (LHSV) is 0.2 and 10hr ^-1Between, most preferably 1.0 and 3.0hr ^-1Between, gas speed 500 and 10000SCFB between, most preferably 1000 and 5000SCFB between.

Being used for the hydrogenant catalyzer is to be usually used in hydrotreated those catalyzer, but contain Pt and/or the Pd catalyzer of unvulcanised are preferred, and Pt and/or Pd are dispersed on carrier such as aluminum oxide, silicon oxide, silica-alumina or the carbon.Preferred carrier is a silica-alumina.

Catalytic dewaxing is made up of the Hydrodewaxing and the hydroisomerization dewaxing of two big class-routines; The hydroisomerization dewaxing can be further divided into part and hydroisomerization dewaxing fully.All kinds of mixtures that make wax shape hydrocarbon stream and hydrogen of all relating to make the n-paraffin in the raw material and the isoparaffin of little branching change into other non-waxy material by the catalyzer that contains acidic components, thereby produce the lube base stock product that pour point can be accepted (being lower than approximately+10 or-12 ℃).All kinds of representative conditions relate to: about 400 to 800 of temperature, and pressure about 200 is to 3000psig, and air speed about 0.2 is to 5hr ^-1For making the raw material selected method that dewaxes typically depend on the wax content of quality product and raw material, conventional Hydrodewaxing generally is preferred for the raw material of low wax content.Selection of catalysts may influence the method for dewaxing.Avilino Sequeira exists Lubricant Base Stock and Wax Processing, Marcel Dekker has carried out comprehensive summary to this theme among the Inc pages 194-223.

Available Santilli etc. are at US5, and the n-hexadecane isomerization test of describing in 282,958 is at conventional Hydrodewaxing, partial hydrogenation isomerization dewaxing and determine the type of dewaxing catalyst fully in the hydroisomerization dewaxing.When under described conditions such as Santilli, measuring with 96% n-hexadecane transformation efficiency, conventional catalyst for hydrogenation de-waxing is lower than 10% to the selectivity of isomerization n-Hexadecane, the hydroisomerization dewaxing catalyst to the selectivity of isomerization n-Hexadecane more than or equal to 10%, partial hydrogenation isomerization dewaxing catalyzer to the selectivity of isomerization n-Hexadecane greater than 10% to less than 40%, fully the hydroisomerization dewaxing catalyst to the selectivity of isomerization n-Hexadecane more than or equal to 40%, be preferably greater than 60%, most preferably greater than 80%.

For this paper, conventional Hydrodewaxing is defined as the catalytic dewaxing process that uses conventional catalyst for hydrogenation de-waxing.In the conventional Hydrodewaxing, reduce pour point by optionally making the cracking of wax molecule, major part is cracked into the less paraffins of boiling point between propane and about octane.Because this technology makes wax change into the lower by product of value, so mainly be applicable to and make the oil dewaxing that does not contain a large amount of waxes.This type of wax shape oil is present in the petroleum distillate (Arabian, North Slope etc.) from medium waxy crude oil usually.The catalyzer that is applicable to conventional Hydrodewaxing is 12-unit ring zeolite and 10-unit ring zeolite normally.This type of zeolite comprises ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35 and mordenite.Conventional catalyst for hydrogenation de-waxing is more conducive to cracking for other method that paraffins is transformed.This n-hexadecane isomerization test with Santilli etc. proves that wherein Chang Gui catalyst for hydrogenation de-waxing is lower than 10% to the selectivity of isomerization n-Hexadecane product.Except that zeolite, can add metal in this catalyzer, be mainly used in the minimizing fouling.Typical process condition, yield and the product property of conventional Hydrodewaxing are described in for example US4,176,050 (Chen etc.), US4,181,598 (Gillespie etc.), US4,222,855 (Pelrine etc.), US4,229,282 (Peters etc.) and US4 are among 211,635 (Chen).These patents are incorporated herein for reference.Sequeira is being entitled as " The Mobil LubeDewaxing Process; " part (p 198-204) and wherein reference J.D.Hargrove, G.J.Elkes, and A.H.Richardson, Oil and Gas J., p.103, Jan.15 further describes and has illustrated processing condition in 1979.

For this paper, the hydroisomerization dewaxing is defined as the catalytic dewaxing process that uses the hydroisomerization dewaxing catalyst.The hydroisomerization dewaxing makes at least a portion of wax change into the isoparaffin of non-waxy by isomerization, reduces this conversion by cracking simultaneously.During to relatively conventional Hydrodewaxing of same materials and hydroisomerization dewaxing, the conversion that wax changes into the non-waxy isoparaffin in the hydroisomerization dewaxing process has the following advantages: the yield of low value by product reduces, the yield of lubricating oil improves and produce VI higher and oxidation and the bigger oil of thermostability.The dual functional catalyst of being made up of acidic components and metal component is used in the hydroisomerization dewaxing.Two components all are that to carry out isomerization reaction needed.Typical metal component is platinum or palladium, and platinum is the most frequently used.The selection of metal and amount are enough to obtain more than 10% isomerized n-Hexadecane product in described tests such as Santilli in the catalyzer.The test of pressing Santilli surpasses at 40% o'clock to the selectivity of n-Hexadecane isomer, and this catalyzer is complete hydroisomerization dewaxing catalyst.Because hydroisomerization dewaxing makes wax change into the isoparaffin of boiling point in the lube base stock scope, so be applicable to and make the oil dewaxing that contains a large amount of waxes.This type of wax shape oil is by from the slack wax of solvent dewaxing process, obtain from the overhead product of high wax content oil (Minas, Altamont etc.) with from the product of Fischer-Tropsch process.

For this paper, the partial hydrogenation isomerization dewaxing is defined as the catalytic dewaxing process that uses partial hydrogenation isomerization dewaxing catalyzer.In the partial hydrogenation isomerization dewaxing, with optionally making the isomerized catalyzer of paraffins make a part of wax be isomerizated into isoparaffin, but the transformation efficiency of wax only remains on than low value (being usually less than 70%).Under the higher situation of transformation efficiency, the wax of realizing by cracking transforms more, and the yield losses of lube base stock becomes uneconomical.An acidic catalyst component that is applicable to the partial hydrogenation isomerization dewaxing comprises amorphous silica alumina, fluorided alumina and 12-unit ring zeolite (as β, Y zeolite, L zeolite).Because wax transforms not exclusively, the partial hydrogenation isomerization dewaxing must be replenished with additional DEWAXING TECHNIQUE (normally solvent dewaxing).Capable of circulation time partial hydrogenation isomerization dewaxing of the wax step that reclaims in the solvent dewaxing operation after the partial hydrogenation isomerization dewaxing.

Typical process condition, yield and the product property of partial hydrogenation isomerization dewaxing are described in for example US5, among 049,536 (Belussi etc.) and the US 4,943,672 (Hamner etc.).These patents are incorporated herein for reference.Further describe and illustrated processing condition among EP 0 582 347 (Perego etc.), EP 0 668 342 (Eilers etc.), PCT WO 96/26993 (Apelian etc.) and the PCT WO 96/13563 (Apelian etc.).

For this paper, the hydroisomerization dewaxing is defined as the catalytic dewaxing process that uses complete hydroisomerization dewaxing catalyst fully.In hydroisomerization dewaxes fully, use complete hydroisomerization dewaxing catalyst, can realize that very high wax transformation efficiency keeps acceptable isomerization selectivity simultaneously.An acidic catalyst component that is applicable to the partial hydrogenation isomerization dewaxing comprises 10-unit ring one dimension molecular sieve (as ZSM-23, SSZ-32, θ-1, ZSM-22, SAPO-11 and SAPO-41).Because it can be completely or at least very high that wax transforms, this method does not need and the acceptable lube base stock of additional process for dewaxing combination results pour point usually.Typical process condition, yield and the product property of hydroisomerization dewaxing are described in for example US5 fully, 135,638 (Miller), US5,246,566 (Miller), US5,282,958 (Santilli etc.), US5,082,986 (Miller) and US5, among 723,716 (Brandes etc.), its content all is incorporated herein for reference.

With the blending of oil blending oil plant

Distillate fuel of the present invention can be made of the composition of blending oil plant, and perhaps described distillate fuel can only not have the fischer-tropsch distillate blending of fuel oil plant of a small amount of additive of optional adding to constitute by there being other blending oil plant.Therefore, described distillate fuel can comprise and oil blending oil plant blended fischer-tropsch distillate blending of fuel oil plant.In the mixture of blending oil plant, preferred described distillate fuel comprises 1 to 95% (weight) fischer-tropsch blending oil plant and 5 to 99% (weight) oil blending oil plant.More preferably described distillate fuel comprises 5 to 75% (weight) fischer-tropsch blending oil plant and 25 to 95% (weight) oil blending oil plant.Even more preferably described distillate fuel comprises 10 to 50% (weight) fischer-tropsch blending oil plant and 90 to 50% (weight) oil blending oil plant.

In addition, in the method for the high paraffinicity of preparation, medium aromaticity content blending oil plant, can make the blending of fischer-tropsch raw material and oil blending oil plant in any stage of described technology, as long as obtain the high paraffinicity of the present invention, medium aromaticity content distillate fuel blending oil plant.For example, can be before the hydrotreatment, after hydrotreatment but before removing polynuclear aromatic hydrocarbons or after removing polynuclear aromatic hydrocarbons but as oil blending oil plant is concocted with Fischer-Tropsch derived feed.Preferably before hydrotreatment, make oil blending oil plant and the blending of fischer-tropsch raw material, then gained concoction stream is carried out hydrotreatment.If the fischer-tropsch raw material mixes with oil blending oil plant, preferred gained tempered oil comprises 1 to 95% (weight) fischer-tropsch raw material and 99 to 5% (weight) oil blending oil plant.More preferably described tempered oil comprises 5 to 75% (weight) fischer-tropsch raw material and 95 to 25% (weight) oil blending oil plant.Even more preferably described tempered oil comprises 10 to 50% (weight) fischer-tropsch raw material and 50 to 90% (weight) oil blending oil plant.

The removal of polynuclear aromatic hydrocarbons

For satisfying the low levels of desired polynuclear aromatic hydrocarbons in high paraffinicity, the medium aromaticity content blending oil plant, the product that can further handle from the hydrotreatment operation flows to remove polynuclear aromatic hydrocarbons.The option of optionally removing polynuclear aromatic hydrocarbons from product stream and keeping the monokaryon aromatic hydrocarbons of wanting comprises the selective hydration processing and adsorbs.

Most preferably being used for flowing the operation of removing polynuclear aromatic hydrocarbons from product is that selective hydration is handled.Reaction conditions and above-mentioned hydrotreated reaction conditions difference that selective hydration is handled are little.The reaction conditions that selective hydration is handled comprise low temperature (be lower than 750 °F, preferably be lower than 700 °F, most preferably be lower than 600 °F), (LHSV is less than 5hr for high pressure (greater than 250psig, be preferably greater than 350psig, most preferably greater than 500psig) and short contacting time ^-1, preferably less than 3hr ^-1, most preferably less than 2hr ^-1).The catalyzer that is preferred for this selective hydration processing comprises Pt, Pd and combination thereof.Selective hydration is handled and will be made polynuclear aromatic hydrocarbons content reduce at least 50% (weight), preferably at least 75% (weight), at least 90% (weight) most preferably, and the decline of monokaryon aromaticity content less than 50% (weight), preferably less than 35% (weight), most preferably less than 20% (weight).

Also can realize from product stream, removing polynuclear aromatic hydrocarbons by going up absorption at oxide carrier, the oxide carrier (acid clay if you would take off stone or attapulgite) that preferably has medium acidity.Adsorption temp should be lower than 200 °F, preferably be lower than 150 °F.Also useable solvents such as N-Methyl pyrrolidone or furfural extraction polynuclear aromatic hydrocarbons.

The interpolation of additive

Described distillate fuel and distillate fuel blending oil plant can comprise the additive that is usually used in diesel oil or jet fuel.Can be used for diesel fuel additive of the present invention such as ChevronCorporation, Technical Review Diesel Fuels, described in the pp.55-64 (2000), can be used for jet fuel additive of the present invention such as ChevronCorporation, Technical Review Aviation Fuels is described in the pp 27-30 (2000).Particularly, these additives can include but not limited to antioxidant (especially low-sulfur antioxidant), oiliness additive and pour point depressant etc.These additives with seldom amount, preferably be lower than 1% (weight) and add in fuel and the blending oil plant.

Particularly, if desired, can improve the stability of the distillate fuel that comprises high paraffinicity, medium aromaticity content blending oil plant or the stability that the present invention concocts oil plant by adding antioxidant.Gasoline and Diesel Fuel Additives, Critical Reports onApplied Chemistry, Vol.25, John Wiley and Sons Publisher, Edited by K.Owen has carried out good summary to fuel with the antioxidant field among pages 4 to 11.

Be applicable to that examples of antioxidants of the present invention includes but not limited to the phenols oxidation retarder, as 4,4 '-methylene radical-two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-two (2-methyl-6-tert butyl phenol), 2,2 '-methylene radical-two (4-methyl-6-tert butyl-phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenols), 4,4 '-isopropylidene-two (2, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene radical-two (4-methyl-6-nonylphenol), 2,2 '-isobutylene-two (4, the 6-xylenol), 2,2 '-methylene radical-two (4-methyl-6-cyclohexylphenol), 2, the 6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol, 2, the 4-dimethyl-6-tertiary butyl-phenol, 2,6-di-t-butyl-dimethylamino-p-cresol, 2,6-two-uncle-4-(N, N '-dimethyl-amino methyl phenol), with two (3,5-di-t-butyl-4-acrinyl).Phenylbenzene amine oxidation retarder includes but not limited to alkylated diphenylamine, phenyl-a-naphthylamine and alkylation-alpha-naphthylamine.Also can use the mixture of compound.The add-on of antioxidant be lower than 500ppm, typically be lower than 200ppm, typically be 5 most to 100ppm.

For example, US4,320,021 (Lange) disclose the amino-phenol of the hydrocarbyl substituent that at least one at least 30 saturated basically carbon atom is arranged.Instruct the amino-phenol of this patent to give oil lubricant and the useful and ideal character of fuel that is generally liquid.Relevant US4 discloses similar amino-phenol among 320,020 (Lange).Similarly, US3,149,933 (Ley etc.) disclose the amino-phenol as the hydrocarbon replacement of liquid fuel stablizer.

US4,386,939 (Lange) disclose the nitrogenous composition of amino-phenol and at least a 3-or 4-unit ring heterocyclic compound prepared in reaction, and wherein said heteroatoms is single oxygen, sulphur or nitrogen-atoms, as oxyethane.Instruct the nitrogenous compound of this patent to be fit to do the additive of lubricant and fuel.

Nitrophenols is also as fuel dope.US4 for example, 347,148 (Davis) disclose and have contained at least one aliphatic substituent nitrophenols at least about 40 carbon atoms is arranged.Instruct the nitrophenols of this patent to be suitable as purification agent, dispersion agent, antioxidant and emulsion splitter and be used for lubricating oil and fuel composition.

Exemplary

Fig. 1 illustrates the preparation method of the high paraffinicity of the present invention, medium aromaticity content distillate fuel blending oil plant.With reference to figure 1, low temperature Fischer-Tropsch derived feed (10) is carried out hydrotreatment in hydrotreater (100), adds hydrogen (20) in this device.Hydroprocessing condition comprises: temperature 600-750 °F, pressure is lower than 1000psig, and liquid hourly space velocity is greater than 0.25hr ^-1Alternatively, in hydrotreatment products (30), add the aromatic hydrocarbons that aromatic hydrocarbons blending oil plant (40) is reformed and obtained as the pure aromatics that is purchased or reformable fischer-tropsch products, obtain containing the high paraffinicity of aromatic hydrocarbons between 2 and 20% (weight), medium aromaticity content distillate fuel is concocted oil plant (50).Described hydrotreatment may produce hydrogen (60), can be at other process such as hydrogen treatment, CO ₂Use in reduction and the fuel production.Alternatively, described high paraffinicity, medium aromaticity content distillate fuel blending oil plant (50) can further be handled in treatment unit (200) to remove polynuclear aromatic hydrocarbons (70) and/or can add antioxidant (80).

Following examples explanation the present invention limits the scope of the invention and should not be construed as.

Embodiment

Embodiment 1: the preparation of diesel oil fuel sample

Synthetic gas is reacted on iron-containing catalyst produce the low temperature fischer-tropsch products.Make this product separation become the blending oil plant (A) and the wax of diesel boiling range.Diesel oil blending oil plant (A) is carried out hydrogen treatment to be removed oxygenatedchemicals and makes alkene saturated.On the sulphurized catalyst of forming by amorphous silica-alumina, aluminum oxide, tungsten and nickel, make the wax hydrocracking.From the effluent of hydrocracker, reclaim the second diesel oil blending oil plant (B).These two kinds blending oil plants are concocted in the ratio of 82% (weight) B and 18% (weight) A.This fischer-tropsch (FT) diesel oil fuel blending oil properties is shown in the Table I.

Table I

Fischer-tropsch diesel oil fuel blending oil properties

Test	The technical requirements of ASTM D975	Fischer-tropsch diesel oil blending oil
			Api gravity, 60 °F		52.3
Nitrogen, NG/UL		0.69
			Cetane value Index A STM D613	40(min)	72.3
Just/non-n-paraffin wt.%
			N-paraffin		17.24
Non-n-paraffin		82.76
			Distillation D86, IBP		333
10％		371
			50％		478
90％	540 (minimums), 640 (maximums)	631
			95％		653
EPT		670

Embodiment 2: the preparation of the tempered oil of fischer-tropsch diesel oil and alkylaromatic hydrocarbon and alkyl naphthene and Estimate

The tempered oil for preparing light alkylaromatic hydrocarbon (cumene) or alkyl naphthene (normenthane) and fischer-tropsch diesel oil fuel blending oil plant.Improvement and the cetane value exponential of measuring sealing swelling and oilness descend.The I of cetane value index decreased is determined preferred alkylaromatic hydrocarbon or the alkyl naphthene selected by seeing which kind of material make the sealing swelling improve maximum.In these experiments the cetane value index be by D2887 distillation, to be converted into D86 equivalent, molecular weight and 20 ℃ of density down definite.This method provides can be accepted and reproducible cetane value exponential measuring result.

The sealing swell test is pressed ASTM D471:

O shape lopps type: Buna N O shape ring, size 2-214; Seller: McDowell ﹠amp; Co.

Test temperature: envrionment temperature 23+/-2 ℃

Duration of test runs: 70 hours

Specimen size: 100ml

The O shape number of rings amount of each sample: 3

The result of report: volume change and changes in hardness

Table II

Conventional petroleum derivation diesel oil fuel expands this type of gasket and long-time back hardening.High parol such as fischer-tropsch fuel do not cause expanding, if in fact gasket is exposed to conventional oil in advance then may causes shrinking.These result's proofs add alkylaromatic hydrocarbon in fischer-tropsch diesel oil blending oil plant or alkyl naphthene makes the gasket swelling in the mode that is similar to conventional oil.Therefore, the tempered oil of high wax distillate blending of fuel oil plant and alkylaromatic hydrocarbon and/or alkyl naphthene in the problem of commercial applications sealing leak still less.In this short-time test process, add alkylaromatic hydrocarbon or alkyl naphthene and do not cause the hardness considerable change.

The contrast of alkylaromatic hydrocarbon of blending shown in Fig. 2 (cumene) and alkyl naphthene (normenthane).Add alkylaromatic hydrocarbon than adding alkyl naphthene more preferably.Producing given volume change needs the alkylaromatic hydrocarbon of less amount, and it is littler to the influence of cetane value index to add alkylaromatic hydrocarbon.

Embodiment 3

On nickelous sulfide-tungsten/silica-alumina catalyzer at LHSV 1hr ^-1, 1000psig, 685 and 6.3MSCF/bb1 condition under make light fischer-tropsch wax (Table III) hydrocracking.Under these conditions, transformation efficiency below 650 is 80.4% (weight).Cut the liquid product cut and obtain diesel oil blending oil plant cut at about 350 °F and about 675 °F.The yield and the character of diesel oil blending oil plant are shown in the Table IV.

Table III

The raw material inspection of light FT wax

Proportion, API	42.5
		Nitrogen, ppm	3.2
Sim.Dist.，LV％，°F
		ST/5	728/771
10/30	789/811
		50	839
70/90	858/885
		95/EP	898/943

Table IV

Light FT wax is at Ni-W-SiO ₂-Al ₂O ₃Go up at LHSV 1hr ^-1, the hydrocracking under 1000psig, 685 and the 6.3MSCF/bb1

Transformation efficiency＜650, wt%	80.4
		Yield, wt%
C 1-C 2	0.03
		C 3-C 4	5.06
C 5-180°F	17.77
		180-350°F	20.85
350-650°F	37.51
		650°F+	19.71
C 5+	95.49
		350-675 character
The wt% of raw material	52.9

Proportion, API	50.7
		Viscosity, 40 ℃, cSt	2.631
Cloud point, ℃	-26
		SFC analyzes, wt%
Aromatic hydrocarbons	0.3
		Alkene	0.8
Oxygenatedchemicals	＜0.1
		Stable hydrocarbon	98.9
PNA aromatic hydrocarbons, wt%	Do not detect
		The cetane value index	75.9
Zhe Guangzhishuo @20 ℃	1.4342
		Density, g/ml@20 ℃	0.7745
Molecular weight	253
		By the carbon type that ndM measures, wt%P/N/A	100/0/0
D2887 Dist.，wt％，°F
		ST/5	288/342
10/30	368/448
		50	523
70/90	594/673
		95/EP	697/743

Supercritical liq chromatography (SFC) detects following 0.5% (weight) that be limited to of PNA.Therefore, the value of not detecting is lower than this amount.Operation only produces 0.3% aromatic hydrocarbons and keeps 0.8% (weight) alkene because of high top pressure operation under these conditions.The paraffinicity of this sample equals saturated hydrocarbon content (98.9).Be applicable to that the ndM that does not contain the alkene sample analyzes demonstration and do not have the naphthenic carbon structure.

Embodiment 4

On the catalyzer identical of sulfurized 3/1 bed/, make with 15% (weight) aluminum oxide adherent Pt/SAPO-11 catalyzer with embodiment 3 with embodiment 3 in identical raw material hydrocracking.Identical among condition and the embodiment 3, promptly total LHSV 1hr ^-1, 1000psig, 685 and 6.3MSCF/bb1H ₂Transformation efficiency below 650 is 74.6% (weight).Cut the product cut and obtain diesel oil blending oil plant cut at about 350 °F and about 650 °F.The yield and the character of diesel oil blending oil plant are shown in the Table V.As measuring by ASTM D6468, this diesel oil blending oil plant is very stable.Because of adopt conventional high top pressure operation and with Pt as catalytic metal, aromatic hydrocarbons accounts for 0.1% (weight) in this diesel oil blending oil plant, alkene accounts for 0.3% (weight).Paraffinicity is 99.6, because do not have naphthenic hydrocarbon by GC-MS mensuration, and obtains ndM analysis support.Cetane value index high (73.8), cloud point extremely low (57 ℃).

Table V

Light FT wax is at 3/1 Ni-W-SiO ₂-Al ₂O ₃/ Pt-SAPO-11 is last at LHSV 1hr ^-1, the hydrocracking under 685,1000psig and the 6.3MSCF/bb1

Transformation efficiency＜650, wt%	74.6
		Yield, wt%
C 1-C 2	0.08
		C 3-C 4	5.16
C 5-180°F	13.02
		180-350°F	15.70
350-650°F	40.97
		650°F+	25.59
C 5+	95.36
		350-650 character
The wt% of raw material	43.1
		Proportion, API	51.3
Viscosity, 40 ℃, cSt	2.206
		Cloud point, ℃	-57
Alkene, wt% (GC-MS)	Do not detect
		PNA aromatic hydrocarbons, wt%	Do not detect
SFC analyzes, wt%
		Aromatic hydrocarbons	0.1
Alkene	0.3
		Oxygenatedchemicals	＜0.1

Stable hydrocarbon	99.6
		The % reflectivity, ASTM D6468@150 ℃
1.5hr	99.7
		3.0hr	99.8
The cetane value index	73.8
		Zhe Guangzhishuo @20 ℃	1.4318
Density, g/ml@20 ℃	0.7699
		Molecular weight	239
By the carbon type that ndM measures, wt%P/N/A	100/0/0
		D2887 Dist.，wt％，°F
ST/5	314/352
		10/30	370/433
50	496
		70/90	549/606
95/EP	629/676

Embodiment 5

Repeat embodiment 4, but stagnation pressure is 500psig in the reactor, temperature of reactor is 680 °F.Transformation efficiency below 650 is 63.5% (weight).Cut the product cut and obtain diesel oil blending oil plant cut at about 350 °F and about 590 °F.The yield and the character of diesel oil blending oil plant are shown in the Table VI.As measuring by ASTM D6468, this diesel oil blending oil plant is very stable.Aromatic hydrocarbons accounts for 2.3% (weight) in this diesel oil blending oil plant.Cetane value index still quite high (69.1), cloud point extremely low (50 ℃).

Table VI

Light FT wax is at 3/1 Ni-W-SiO ₂-Al ₂O ₃/ Pt-SAPO-11 is last at LHSV 1hr ^-1, the hydrocracking under 680,500psig and the 6.3MSCF/bb1

Transformation efficiency＜650, wt%	63.5
		Yield, wt%
C 1-C 2	0.23
		C 3-C 4	10.53
C 5-180°F	13.98

180-350°F	15.63
		350-650°F	23.72
650°F+	36.75
		C 5+	90.0
350-590 character
		The wt% of raw material	19.1
Proportion, API	51.1
		Viscosity, 40 ℃, cSt	1.94
Cloud point, ℃	-50
		PNA aromatic hydrocarbons, wt%	Do not detect
The % reflectivity, ASTM D6468@150 ℃
		1.5hr	99.7
3.0hr	99.7
		The cetane value index	69.1
Zhe Guangzhishuo @20 ℃	1.4323
		Density, g/ml@20 ℃	0.7704
Molecular weight	224
		D2887 Dist.，wt％，°F
ST/5	316/350
		10/30	366/415
50	468
		70/90	519/572
95/EP	591/643

Embodiment 6

Catalyst body at the embodiment 2 of same bed is fastened FT wax (Table VII) hydrocracking that 700-1000 hydrogen treatment crossed.Condition comprises total LHSV 1.0hr ^-1, reactor pressure 300psig, 680 top of catalyzer, following 690 of catalyzer and 6.3MSCF/bb1H ₂Transformation efficiency below 650 is 58.2% (weight).Cut the product cut and obtain diesel oil blending oil plant cut at about 300 °F and about 650 °F.The yield and the character of diesel oil blending oil plant are shown in the Table VIII.As measuring by ASTM D6468, this diesel oil blending oil plant is very stable.Aromatic hydrocarbons accounts for 4.3% (weight) in this diesel oil blending oil plant, and alkene accounts for 1.0% (weight), and oxygenatedchemicals accounts for 0.5% (weight).Paraffin equates (94.2%) with stable hydrocarbon because the GC-MS technology do not detect the alkene of obvious amount and naphthenic hydrocarbon each.Cetane value index height (67.6), cloud point are-44 ℃.

Table VII

The raw material inspection of the FT wax that 700-1000 hydrogen treatment crossed

Proportion, API	42.3
		Sim.Dist.，LV％，°F
ST/5	691/804
		10/30	824/884
50	919
		70/90	940/974
95/EP	991/1031

Table VIII

The FT wax that 700-1000 hydrogen treatment crossed is at 3/1 Ni-W-SiO ₂-Al ₂O ₃/ Pt-SAPO-11 is last at LHSV 1hr ^-1, the hydrocracking under 680/690,300psig and the 6.3MSCF/bb1

Transformation efficiency＜650, wt%	58.2
		Yield, wt%
C 1-C 2	0
		C 3-C 4	4.78
C 5-180°F	14.93
		180-350°F	15.53
350-650°F	23.22
		650°F+	41.92
C 5+	95.7
		350-650 character
The wt% of raw material	31.1
		Proportion, API	50.1

Viscosity, 40 ℃, cSt	2.027
		Cloud point, ℃	-44
Naphthenic hydrocarbon+alkene, wt% (GC-MS)	Do not detect
		SFC analyzes, wt%
Aromatic hydrocarbons	4.3
		Alkene	1.0
Oxygenatedchemicals	0.5
		Stable hydrocarbon	94.2
PNA aromatic hydrocarbons, wt%	0.5
		The % reflectivity, ASTM D6468@150 ℃
1.5hr	99.2
		3.0hr	99.2
The cetane value index	67.6
		Zhe Guangzhishuo @20 ℃	1.4348
Density, g/ml@20 ℃	0.7741
		Molecular weight	196
D2887 Dist.，wt％，°F
		ST/5	266/300
10/30	325/396
		50	472
70/90	561/645
		95/EP	667/698

When down measuring 180 minutes by ASTM D6468 for 150 ℃, the diesel oil blending oil plant of embodiment 6 demonstrates excellent stability, and embodiment 4 and 5 diesel oil blending oil plant also demonstrate excellent stability, and the result surpasses 99%.The polynuclear aromatic hydrocarbons content of the diesel oil blending oil plant of embodiment 6 is lower than 12% (weight) of total aromatic hydrocarbons (4.3%).

Below be a series of Comparative Examples, illustrate that untreated fischer-tropsch products is being unsettled aspect the formation superoxide, conventional hydrotreatment operation is created in and forms the stable extremely low product of unsaturated hydrocarbons content in superoxide aspect.

The preparation of the complete hydrogenant diesel oil blending of Comparative Examples 7-oil plant

By the three kinds of high paraffin diesel oil blending of low temperature fischer-tropsch feedstock production oil plants.

Table I X-fischer-tropsch raw material properties

Character	Raw material 1	Raw material 2	Raw material 3
				Wt% in tempered oil	27.8	23.1	49.1
Proportion, ° API	56.8	44.9	40.0
				Sulphur, ppm	＜1	＜1
Oxygen, ppm passes through Neut.Act.	1.58	0.65
				Chemical type, wt% passes through GC-MS
Paraffins	38.4	62.6	85.3
				Alkene	49.5	28.2	1.6
Alcohol	11.5	7.3	9.3
				Other material	0.5	3.9	3.8
The D-2887 distillation, wt%, °F
				0.5/5	80/199	73/449	521/626
10/30	209/298	483/551	666/758
				50	364	625	840
70/90	417/485	691/791	926/1039
				95/99.5	518/709	872/1074	1095/1184

Flow downward and prepare the blending oil plant continuously by supplying different raw materials by hydrotreating reactor.Reactor is filled with the catalyzer that comprises aluminum oxide, silicon oxide, nickel and tungsten.Make this catalyst vulcanization before the use.Make 665-710 the per pass conversion below the circulation cut point be maintained at about 80% by regulating catalyst temperature.

To obtain gaseous by-product, light naphtha fraction, diesel oil blending oil plant cut and unconverted cut from the product continuous still battery of hydrotreating reactor behind the separation and the unreacted hydrogen that circulates.Unconverted cut loops back hydrotreating reactor.The temperature of regulating distillation tower makes flash-point and cloud point remain on the target value of 58 ℃ and-18 ℃ respectively.

Under 1.4LHSV, raw material concocted the A of the typical products in the Table X was provided in several hours.

The character of the distillate fuel blending oil product of Table X-blending

Oxygen can organic oxygen-containing compound (measuring by vapor-phase chromatography-mass spectroscopy (GC-MS)), dissolving or dispersive water (measuring by Karl Fischer) or from the dissolving O of air ₂Form is present in the sample.

The content of oxygenatedchemicals is measured by GC-MS.Handle oxygenatedchemicals in the sample to improve the sensitivity of this technology with tetraethoxysilane (TEOS).Can not detect oxygenatedchemicals in the product A.Determine that detecting of this technology is limited to the 6.5ppm/ oxygenatedchemicals.In the molecular weight ranges of diesel oil fuel, this is equivalent to the oxygen of 0.6ppm oxygenatedchemicals form.Suppose that the 10 kinds of oxygenatedchemicalss of having an appointment in the typical sample just are lower than this detection limit, then the maximum of the oxygen of oxygenatedchemicals form is 6ppm (0.0006wt%) in the sample.

Utilize O in the pure compound ₂Dissolubility data is estimated the O from air ₂Solubleness in product A is about 92ppm (0.0092wt%).There is not easy-to-use measurement dissolving O ₂Method.GC-MS analyzes and is shown among the Table X I.

The GC-MS of Table X I-distillate fuel blending oil plant analyzes

Molecular formula	N-paraffin area %	Branched paraffin area %	Total paraffinic hydrocarbons	I/n (carbon number)
					C 9H 20	2.96	0.00	2.96	-
C 10H 22	3.59	4.24	7.83	1.18
					C 11H 24	3.80	4.65	8.45	1.22
C 12H 26	3.65	4.77	8.42	1.31
					C 13H 28	3.41	5.34	8.75	1.57
C 14H 30	3.00	5.34	8.34	1.78
					C 15H 32	2.61	5.56	8.17	2.13
C 16H 34	2.33	8.65	10.98	3.71
					C 17H 36	1.99	5.74	7.72	2.89
C 18H 38	1.51	6.11	7.62	4.04
					C 19H 40	1.60	5.98	7.58	3.73
C 20H 42	1.18	5.35	6.53	4.52
					C 21H 44	0.58	3.82	4.41	6.54
C 22H 46	0.22	2.00	2.23	8.94

The % paraffins	100.00
		% alkene	0.00
Average carbon number	15.12
		The boiling point of average carbon number, °F	521
The ratio of the paraffinic hydrocarbons i/n of bulk sample	2.08

As mentioned above, do not detect oxygenatedchemicals in the product A.And product A contains and is less than 1% (weight) aromatic hydrocarbons.Lacking aromatic hydrocarbons further improves the possibility of the rapid oxidation of product A.

The preparation of Comparative Examples 8-alkene diesel oil fuel blending oil plant

In this example, make the raw material 1 of fischer-tropsch blending oil plant among the Table I X walk around hydrotreater and directly infeed distillation tower.Use with embodiment 7 in identical catalyzer and condition (comprising LHSV1.4), the condition of regulating distillation tower is with identical product flash-point and cloud point among the maintenance embodiment 7.Owing to need to reduce the terminal point of diesel oil fuel blending oil plant to keep cloud point, so the yield of diesel oil fuel blending oil plant is lower, near 73%.

Diesel oil fuel is concocted oil plant concoct several hours so that the B of the typical products in the Table X to be provided.The operation that all infeeds hydrotreater with all fischer-tropsch logistics is opposite, walks around the terminal point lower yield reduction that cause diesel oil fuel blending oil plant of described light constituent because of diesel oil.The diesel oil terminal point is low may to be the higher result of heavy n-paraffin concentration in the product B.The GC-MS of product B analyzes and is shown among the Table X II.

The GC-MS of Table X II-product B analyzes

Carbon number	The 1-alkene	The n-paraffinic hydrocarbons	The i-paraffinic hydrocarbons	Alcohol	Summation	Paraffinic hydrocarbons i/n ratio
							C 6	0.00	0.00	0.00	0.03	0.03
C 7	0.00	0.00	0.00	0.21	0.21
							C 8	0.00	0.00	0.00	0.32	0.32
C 9	2.49	2.49	2.13	0.21	7.32	0.86
							C 10	3.55	3.20	4.62	0.12	11.49	1.44
C 11	3.91	3.91	4.97	0.03	12.82	1.27
							C 12	3.55	4.26	4.62	0.09	12.52	1.08
C 13	2.35	4.36	4.69	0.00	11.39	1.08
							C 14	1.68	4.69	4.02	0.00	10.39	0.86
C 15	0.00	4.36	6.03	0.00	10.39	1.38
							C 16	0.00	4.36	4.02	0.00	8.38	0.92
C 17	0.00	4.36	3.35	0.00	7.71	0.77
							C 18	0.00	3.02	1.68	0.00	4.69	0.56
C 19	0.00	1.34	1.01	0.00	2.35	0.75
							Summation	17.52	40.32	41.14	1.02	100.00

The % paraffins	81.46
		% alkene	17.52
Average carbon number	13.20
		The oxygen of oxygenatedchemicals form, ppm	1226
The paraffinic hydrocarbons i/n ratio of bulk sample	1.02

These results also show: hydrotreating reactor is walked around in a part of fischer-tropsch logistics and when sneaking into final blending oil product, the blending oil product comprises a large amount of alkene.In fact alkene is Duoed 10 times than alcohol in this blending oil product.Alkene and oxygenatedchemicals bring the potential stability problem.

The measurement of embodiment 9 stability

Product B is pressed ASTM D6468 and was tested 180 minutes down at 150 ℃, and recording stability is 99.3%, shows that it is being a stabilizer pole for forming settling in this test.

Press US6 then, 162,956 and 6,180, these products of method test described in 842 are in the formation amount of quickening superoxide under the formation condition.Test these products according to the standard method of measuring the superoxide accumulation volume.At first, 4 ounces of samples are placed in the brown bottle, inflated 3 minutes.Test the peroxide level of a five equilibrium sample then by ASTM D3703.The peroxide level of sample is measured with the method for ASTM D3703, but replaces the freonll-11 solvent with octane-iso.Then sample is built, in 60 ℃ of baking ovens, placed for 1 week.Replicate measurement peroxide number and make sample return baking oven after at this moment.This operation is carried out weekly once obtaining final peroxide number until through 4 weeks.Table X III comprises superoxide and forms tendency.

Table X III-superoxide forms tendency

	A	B
			The initial peroxide value	1.3	8.2
Peroxide number after 60 ℃ of following 1 weeks	1.0	35
			Peroxide number after 60 ℃ of following 2 weeks	1.5	156
Peroxide number after 60 ℃ of following 3 weeks	1.88	204
			Peroxide number after 60 ℃ of following 4 weeks	＜5	＞5

Another test of product A is carried out under 70 ℃.Initial peroxide value and the peroxide number after 4 weeks are all less than 1ppm.These results show that product A has obviously than the better peroxide stability of product B.These test-results prove that the distillate fuel blending oil plant of the stability of complete hydrogenant low temperature fischer-tropsch products and the fischer-tropsch logistics that comprises not hydrotreatment forms the tendency of superoxide fast.

Embodiment 10-trace alkene is to the influence of peroxide stability

Further determine the influence that in the stable blending oil plant product A of Table X, adds the small amounts of olefins condensation product.Obtain 300-600 the part (raw material 1 of Table I X) of cryogenic condensation thing by distillation.The character of the 300-600 of this condensation product part is as follows:

The character of the 300-600 of Table X IV-condensation product part

Character	Value
		Api gravity	65.3
Nitrogen, ppm	0.79
		Sulphur, ppm	2.29
Bromine number	48.2
		Simulation distil, D-2887, °F, wt%
0.5/5％	296/302
		10/30％	332/383
50％	393
		70/90％	459/523
95/99.5％	551/654

The GC-MS of the 300-600 of this condensation product part analyzes and obtains these results (wt%):

The GC-MS of the 300-600 of this condensation product of Table X V-part analyzes

Carbon number	The n-paraffinic hydrocarbons	Paraffinic hydrocarbons	Alcohol	Summation
					C 6	0.00	0.00	0.00	0.00
C 7	0.00	0.00	1.54	1.54
					C 8	0.00	0.00	0.32	0.32
C 9	2.20	3.30	1.32	6.82
					C 10	12.37	5.35	1.03	18.75
C 11	11.46	5.28	0.81	17.54
					C 12	10.37	5.94	0.54	16.85
C 13	8.43	5.72	0.29	14.44
					C 14	5.85	4.69	0.19	10.74
C 15	3.31	3.01	0.00	6.32
					C 16	1.60	1.76	0.00	3.36
C 17	0.73	0.95	0.00	1.69
					C 18	0.34	0.55	0.00	0.89
C 19	0.15	0.33	0.00	0.48
					C 20Summation	0.06 56.87	0.21 37.10	0.00 6.03	0.26 100.00

The % paraffins	37.10
		% alkene	56.87
Average carbon number	12.03
		Standard deviation	2.10
％C 12-C 24Material	55.02
		The oxygen of oxygenatedchemicals form, ppm	6769
C 12-C 24The oxygen of primary alconol form, ppm	832
		C 7-C 12The oxygen of primary alconol form, ppm	6398

Embodiment 11

Make the steady fuel blending oil plant A blending of 300-600 part of described condensation product with different amounts and Table X, the superoxide of estimating this tempered oil forms tendency, and the result is as follows:

The superoxide of Table X VI-tempered oil 1-5 forms tendency

These results show that the blending oil plant by whole hydrogen treatment (not having the direct blending of condensation product) preparation is being stable aspect the formation superoxide.The blending oil plant can only be tolerated maximum 0.2% (weight) condensation product (0.012wt% is by oxygenatedchemicals and about 0.1wt% alkene of the pure form of GC-MS mensuration) and still think stable.There is blending oil plant not demonstrate gratifying stability more than 0.012wt% oxygenatedchemicals or 0.1wt% alkene.When oxygenates level surpassed 0.012wt%, the peroxide stability of blending oil plant descended rapidly.

Though at length and in conjunction with specific embodiments invention has been described, can under the situation that does not deviate from its spirit and scope, carry out various changes and revise apparent to those skilled in the art.

Claims (29)

1. a distillate fuel comprises fischer-tropsch distillate blending of fuel oil plant, and wherein said fischer-tropsch distillate blending of fuel oil plant comprises:

A) aromatic hydrocarbons between 2 and 20 weight %; With

B) 80 weight % or more paraffin;

C) greater than 60 cetane value index; With

D) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.25% volume change by ASTM D471 with Buta N nitrile O shape.

2. the fuel of claim 1, nearly 100 weight % of wherein said distillate fuel are fischer-tropsch distillate blending of fuel oil plants.

3. the fuel of claim 1 also comprises oil blending oil plant.

4. the fuel of claim 3, wherein said fuel comprise 5 to 75 weight % fischer-tropsch distillate blending of fuel oil plants and 95 to 25 weight % oil blending oil plant.

5. the fuel of claim 1, at least a portion of wherein said aromatic hydrocarbons come from aromatic hydrocarbons blending oil plant.

6. the fuel of claim 1, wherein said fischer-tropsch distillate blending of fuel oil plant is included in the aromatic hydrocarbons between the 2 and 15 weight %.

7. the fuel of claim 1, wherein said fischer-tropsch distillate blending of fuel oil plant is included in the aromatic hydrocarbons between the 5 and 10 weight %.

8. the fuel of claim 1, wherein said fischer-tropsch distillate blending of fuel oil plant comprise at least 0.5% the volume change of measuring by ASTM D471.

9. the fuel of claim 1, wherein said fischer-tropsch distillate blending of fuel oil plant comprise at least 2% the volume change of measuring by ASTM D471.

10. the fuel of claim 1, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is less than 20 weight %.

11. the fuel of claim 1, wherein said distillate fuel also comprises the sulphur that is lower than 1ppm.

12. the fuel of claim 1, wherein said distillate fuel also comprises the nitrogen that is lower than 1ppm.

13. the fuel of claim 1, wherein said distillate fuel also comprises antioxidant.

14. the fuel of claim 1, wherein said distillate fuel meet at least one technical requirements of diesel oil or jet fuel.

15. the fuel of claim 14, wherein said distillate fuel meet at least one technical requirements of diesel oil fuel, and the cetane value index is greater than 65.

16. pressing ASTM D6468 reflectivity when measuring 90 minutes down for 150 ℃, the fuel of claim 15, wherein said fuel surpasses 65%.

17. the fuel of claim 14, wherein said distillate fuel meet at least one technical requirements of jet fuel, 260 ℃ were tested and appraised in following 2.5 hours in ASTM D 3241.

18. a fischer-tropsch diesel oil fuel blending oil plant comprises:

A) aromatic hydrocarbons between 5 and 10 weight %, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20 weight %;

B) 90 weight % or more paraffin;

C) be lower than the sulphur of 1ppm;

D) greater than 60 cetane value index;

E) press ASTM D6468 when measuring 90 minutes down for 150 ℃, surpass 65% reflectivity; With

F) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.5% volume change by ASTM D471 with Buta N nitrile O shape.

19. the blending oil plant of claim 18, the cetane value index of wherein said blending oil plant is greater than 65.

20. the blending oil plant of claim 18, the cetane value index of wherein said blending oil plant is greater than 70.

21. the blending oil plant of claim 18, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 10 weight %.

22. a fischer-tropsch jet fuel blending oil plant comprises:

A) aromatic hydrocarbons between 5 and 10 weight %, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 20 weight %;

B) 90 weight % or more paraffin;

C) be lower than the sulphur of 1ppm;

D) 30mm or bigger smoke point;

E) in ASTM D 3,241 260 ℃ be tested and appraised in following 2.5 hours; With

F) encircle ℃ measurement in following 70 hours in 23+/-2, at least 0.5% volume change by ASTM D471 with Buta N nitrile O shape.

23. the blending oil plant of claim 22, wherein said blending oil plant in ASTM D3241 270 ℃ be tested and appraised in following 2.5 hours.

24. the blending oil plant of claim 22, wherein said aromatic hydrocarbons comprises the polynuclear aromatic hydrocarbons that is lower than 10 weight %.

25. the working method of a diesel motor comprises with the fischer-tropsch blending oil plant of claim 18 and makes diesel oil fuel.

26. the diesel motor working method of claim 25, wherein said diesel oil fuel also comprise oil blending oil plant.

27. the diesel motor working method of claim 25, wherein said diesel oil fuel also comprises antioxidant.

28. the working method of a jet engine comprises with the fischer-tropsch blending oil plant of claim 22 and makes jet fuel.

29. the jet engine working method of claim 28, wherein said jet fuel also comprise oil blending oil plant.

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