CN1839196A - Stable, moderately unsaturated distillate fuel blend stocks prepared by low pressure hydroprocessing of fischer-tropsch products - Google Patents
Stable, moderately unsaturated distillate fuel blend stocks prepared by low pressure hydroprocessing of fischer-tropsch products Download PDFInfo
- Publication number
- CN1839196A CN1839196A CNA2004800238847A CN200480023884A CN1839196A CN 1839196 A CN1839196 A CN 1839196A CN A2004800238847 A CNA2004800238847 A CN A2004800238847A CN 200480023884 A CN200480023884 A CN 200480023884A CN 1839196 A CN1839196 A CN 1839196A
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- raw material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a distillate fuel comprising a stable, low sulfur, highly paraffinic, moderately unsaturated distillate fuel blend stock. The highly paraffinic, moderately unsaturated distillate fuel blend stock exhibits excellent combustion properties in diesel and jet engines as a result of the high paraffin content. The blend stock is preferably prepared from a Fischer-Tropsch derived product that is hydroprocessed under conditions during which a moderate amount of unsaturates are formed or retained.
Description
Related application
The application is the U. S. application No.09/999 of being entitled as of submitting to October 19 calendar year 2001 " the distillate fuel tempered oil of the sealing swelling property that improvement is arranged that is obtained by Fischer-Tropsch process product ", 667 part continuation application, so its disclosure is incorporated into as a reference.The application also with the U.S. Patent application No.10/464 of being entitled as of submitting to simultaneously " the height paraffin of the low-voltage hydrogenation operation preparation by Fischer-Tropsch process product, the distillate fuel blending raw material that the moderate virtue belongs to ", 546 (Docket No.005950-779) are relevant.
Invention field
The present invention relates to a kind of low-sulfur distillate fuel that contains Fischer-Tropsch process distillate fuel blending raw material, this low-sulfur distillate fuel has the excellent stability and the unsaturated compound content of moderate.
Background of invention
The distillate fuel that Fischer-Tropsch process obtains is a height paraffin, and excellent combustionproperty and very low sulphur content are arranged.This is ideally suited in environmental problem Fischer-Tropsch process product is that the area of major issue is as fuel.Have the fuel of good stability or preferred excellent stability always to wish, stable fuel can be produced by the hydrotreatment or the hydrocracking of Fischer-Tropsch process product.But traditional hydrotreatment and hydrogenolysis need use expensive hydrogen to make alkene saturated and oxygenate become alkane.
Because its low emission and good motor performance have the stable diesel oil fuel of low sulfur content and high cetane index to wish.Equally, there is the stable rocket engine fuel of low sulfur content and high smoke point also to wish.This class A fuel A can be by Fischer-Tropsch process product production.It is known producing distillate fuel by the Fischer-Tropsch process method.
Though Fischer-Tropsch process product is a height paraffin, they also contain other compound of the caused stability problem of alkene, alcohols and trace.Usually, hydroprocessing is used to make basically all alkene saturated and remove oxygenatedchemicals.But hydroprocessing need use expensive hydrogen and under high pressure operating the equipment that designs.
The stability measurement of corresponding fuel has been described about the ASTM technical specification (D985) of diesel oil fuel.For diesel oil fuel, ASTM D6468, " standard test methods of distillate fuel high-temperature stability " just is being considered as the standard test methods of diesel oil fuel, and this test can provide the good measure of fuel stability.In this test, the Fischer-Tropsch process product of pure hydrotreatment and hydrocracking has fabulous stability usually.The application of testing ASTM D3241 at 260 ℃ of qualified down JFTOT has been described about the ASTM technical specification (D 1655) of rocket engine fuel A and A-1.Higher stability is usually wished.For example, Colonial Pipeline ' the s Quality Assurance guidelines (3.19.1 part, 3B-33 page or leaf) since in February, 2003 requires alternative aviation kerosene that 275 ℃ or higher JFTOT stability are arranged.This advantages of higher stability requires and will provide some compensation to the stability decreases of product in shipment.The Coordinating Research Council ' s
Handbook of Aviation Fuel PropertiesThird Printing, May 1988 the 102nd page (table 10) points out that several military jet fuels have higher stability requirement: JP-9 and JP-10 to require 300 ℃ or higher stability than commercial Jet A, and JP-7 and TS require 335 ℃ or higher stability.The rocket engine fuel of high stable is normally wished.
Except traditional stability (thermostability and package stability) is measured, the research of Vardi etc. (J.Vardi and B.J.Kraus, " generation of superoxide in low-sulfur motor vehicle diesel fuel ", February 1992, SAE Paper 920826) described how fuel produces a large amount of superoxide in storage process and how these superoxide can corrode fuel system elastomerics (O type ring, flexible pipe etc.).The available infrared spectra of the generation of superoxide, chemical process or measure by erosion to elastomer sample.Point out that as Vardi etc. when its sulphur content is dropped to when low-level, with regard to the generation of superoxide, fuel variable gets unstable.Vardi etc. point out also with regard to the generation of superoxide, how the compound resemble the 1,2,3,4-tetralin makes fuel become unstable, and the polynuclear aromatic compound resemble the naphthalene can improve stability.Explanation aromatic hydrocarbons such as Vardi play natural antioxidants and point out to remove natural superoxide inhibitor for example sulphur compound and polycyclic aromatic hydrocarbons.
After the work of Vardi, it is how unacceptable that two pieces of up-to-date patents of Exxon have been described the peroxide stability of Fischer-Tropsch process product of height paraffin, but can improve by adding the sulphur compound that obtains from other blending component.But, because sulphur compound increases the quantity discharged of sulphur, so this approach is undesirable.
As an example, U.S. patent No.6,162,956 disclose the cut that distillates that Fischer-Tropsch process that a kind of and the condensation of dirt gas field distillate cut or slight hydrotreatment condensate fraction blending obtains, and make stable downtrod distillate fuel.Described fuel is called as the suitable blending component of making the blending raw material of distillate fuel or being used for distillate fuel, and distillate fuel contains: (a) contain C
8The cut that the Fischer-Tropsch process of-700 cuts obtains and (b) contain C
8The natural-gas field condensate fraction of-700 cuts, the sulphur content of wherein concocting raw material by weight 〉=1ppm.The distillate fuel that this patent disclosure, Fischer-Tropsch process obtain is removed unsaturated materials through hydrotreatment, for example alkene and most of oxygenatedchemicals (if not whole words).This patent is further open, and product contains and is less than or equal to 0.5 weight % unsaturated compound (alkene and aromatic hydrocarbons).
Equally, U.S. patent No.6,180,842 Fischer-Tropsch processes that disclose the straight run condensation products blending of a kind of and thick straight run condensate fraction or slight hydrotreatment obtain distillates cut, to make stable downtrod distillate fuel.Described fuel is called as the suitable blending component of making the blending raw material of distillate fuel or being used for distillate fuel, and described fuel contains (a) and contains C
8The distillate that the Fischer-Tropsch process of-700 logistics obtains (sulphur content is by weight less than 1ppm) and (b) 1-40 weight % contain C
8The straight run oil of-700 logistics; The sulphur content of wherein concocting raw material by weight 〉=2ppm.This patent points out though there is not the standard of fuel peroxide level, general approval is arranged, that is, the peroxide value of steady fuel is wished less than about 1ppm less than about 5ppm, preferably less than about 4ppm.This numerical value is tested stored for 4 weeks in 60 ℃ of stoves after.Described patent shows, 4 week the back peroxide values be that 24.06 Fischer-Tropsch process product has unacceptable stability.
Fischer-Tropsch process product in ' 842 patents is described to＞80 weight %, preferred＞90 weight %, more preferably＞95 weight % alkane, and isomery/positive structure is than being 0.1-10, preferred 0.3-3.0, more preferably 0.7-2.0; Sulphur and nitrogen separately less than 1ppm, preferably less than 0.5ppm, more preferably separately less than 0.1ppm; Unsaturated compound (alkene and aromatic hydrocarbons)≤0.5 weight %, preferred≤0.1 weight %; And by anhydrous benchmark, oxygen less than 0.5 weight %, preferably less than about 0.3 weight %, be more preferably less than 0.1 weight %, most preferably do not have oxygen.' 842 patent disclosures, the Fischer-Tropsch process cut is substantially free of acids.
U.S. patent No.5, the alkene of 689,031 proofs in low sulphur diesel fuel helps the generation of superoxide.Referring to the fuel C among the embodiment 7 and D and Fig. 2.The terms of settlement that ' 031 patent disclosure, superoxide generate tendency is will be by light olefin cut fraction hydrogenation is handled the content that limits alkene.But this terms of settlement need be used expensive hydrogen.
Therefore, in this specialty, low-sulfur distillate fuel and the distillate fuel blending raw material with gratifying stability there is demand, described low-sulfur distillate fuel and distillate fuel blending raw material can be made by Fischer-Tropsch process product, and the use of expensive hydrogen is minimized.The invention provides such distillate fuel and distillate fuel blending raw material and production method thereof.
Summary of the invention
The present invention relates to a kind of distillate fuel that contains Fischer-Tropsch process distillate fuel blending raw material.Described Fischer-Tropsch process distillate fuel blending raw material contains unsaturated compound, content that content is 2-20 weight % be 80 weight % or bigger alkane, content less than the sulphur of 1ppm and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide, and the cetane index of described Fischer-Tropsch process distillate fuel blending raw material is greater than 60.
In another embodiment, the present invention relates to a kind of Fischer-Tropsch diesel fuels blending of fuel raw material.It is that 90 weight % or bigger alkane, content make that less than sulphur and the content of 1ppm generation is less than the peroxide precursor of 5ppm superoxide after storing for 4 weeks under 60 ℃ that described Fischer-Tropsch diesel fuels blending of fuel raw material contains unsaturated compound, the content that content is 2-20 weight %.Described unsaturated compound contains less than 20 weight % polycyclic aromatic hydrocarbonss, preferably less than 10 weight % polycyclic aromatic hydrocarbonss even be more preferably less than 5 weight % polycyclic aromatic hydrocarbonss.Preferably, unsaturated compound not only comprises alkene but also comprise aromatic hydrocarbons, and most preferably, the content of alkene is more than or equal to 1 weight %.Diesel oil fuel blending Material Characteristics comprises cetane index greater than 60, and when when measuring in 90 minutes, 150 ℃ of percentage reflectivity of pressing ASTM D6468 down surpass 65%.
In another embodiment, the present invention relates to a kind of Fischer-Tropsch process rocket engine fuel blending raw material.Described Fischer-Tropsch process rocket engine fuel blending raw material contains unsaturated compound, content that content is 2-10 weight % be 90 weight % or bigger alkane, content less than the sulphur of 1ppm and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide.Described unsaturated compound contains less than 20 weight % polycyclic aromatic hydrocarbonss, preferably less than 5 weight % polycyclic aromatic hydrocarbonss even be more preferably less than 5 weight % polycyclic aromatic hydrocarbonss.Rocket engine fuel blending Material Characteristics comprises that smoke point is 30 millimeters or bigger, and the acceptance value (passing rating) among the ASTM D 3241 (JFTOT program) was at 260 ℃, 2.5 hours.
In another embodiment, the present invention relates to a kind of method for preparing height paraffin, moderate unsaturated distillate blending of fuel raw material.Described method comprises: by Fischer-Tropsch process synthetic gas is changed into the raw material that Fischer-Tropsch process obtains, and the raw material that described Fischer-Tropsch process obtains is carried out hydroprocessing.Reclaim height paraffin, moderate unsaturated distillate blending of fuel raw material.Described height paraffin, moderate unsaturated distillate blending of fuel raw material contain 2-20 weight % unsaturated compound, make that less than 1ppm sulphur and content generation is less than the peroxide precursor of 5ppm superoxide after storing for 4 weeks under 60 ℃.The hydroprocessing condition comprises that temperature is 600-750 , pressure less than 1000psig and liquid hourly space velocity greater than 0.25 hour
-1
In another embodiment, the present invention relates to a kind of distillate fuel that contains Fischer-Tropsch process distillate fuel blending raw material, wherein said Fischer-Tropsch process distillate fuel blending raw material prepares by the following method, and described method comprises by Fischer-Tropsch process synthetic gas is changed into the raw material that Fischer-Tropsch process obtains; The raw material that described Fischer-Tropsch process is obtained is at temperature 525-775 , pressure less than 1000psig and liquid hourly space velocity greater than 0.25 hour
-1Following hydroprocessing; And reclaim the Fischer-Tropsch process distillate fuel and concoct raw material.The Fischer-Tropsch process distillate fuel that reclaims is concocted raw material and is contained 2-20 weight % unsaturated compound, makes that less than 1ppm sulphur and content the back generation of 4 week of storage is less than the peroxide precursor of 5ppm superoxide under 60 ℃.
In another embodiment, the present invention relates to a kind of method of operating diesel engines, described method comprises uses Fischer-Tropsch process diesel oil fuel blending raw material as diesel oil fuel, wherein said Fischer-Tropsch diesel fuels blending of fuel raw material contains unsaturated compound, content that content is 2-20 weight % be 90 weight % or more alkane, content less than the sulphur of 1ppm and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide.Described unsaturated compound contains less than 20 weight % polycyclic aromatic hydrocarbonss, preferably less than 10 weight % polycyclic aromatic hydrocarbonss even be more preferably less than 5 weight % polycyclic aromatic hydrocarbonss.Preferably, unsaturated compound not only comprises alkene but also comprise aromatic hydrocarbons, and most preferably, the content of alkene is more than or equal to 1 weight %.Diesel oil fuel blending Material Characteristics comprises cetane index greater than 60, and when when measuring in 90 minutes, 150 ℃ of percentage reflectivity of pressing ASTM D6468 down surpass 65%.
In another embodiment, the present invention relates to a kind of method of operating jet engine, described method comprises uses Fischer-Tropsch process rocket engine fuel blending raw material as rocket engine fuel, wherein said Fischer-Tropsch process rocket engine fuel blending raw material contains unsaturated compound, content that content is 2-10 weight % be 90 weight % or more alkane, content less than the sulphur of 1ppm and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide.Described unsaturated compound contains less than 20 weight % polycyclic aromatic hydrocarbonss, preferably less than 5 weight % polycyclic aromatic hydrocarbonss even be more preferably less than 5 weight % polycyclic aromatic hydrocarbonss.Rocket engine fuel blending Material Characteristics comprises that smoke point is 30 millimeters or bigger, and the acceptance value among the ASTM D3241 (JFTOT program) was at 260 ℃, 2.5 hours.
The accompanying drawing summary
Accompanying drawing is the explanation to the method for producing distillate fuel blending raw material of the present invention.
Detailed Description Of The Invention
According to the present invention, found to produce low-sulfur, height paraffin, moderate unsaturated distillate blending of fuel raw material, described distillate fuel blending raw material has excellent stability. Described distillate fuel blending raw material can be produced with a kind of like this method, and described method comprises the synthetic and equivalent unsaturated compound or keep hydroprocessing under the condition of moderate unsaturated compound in product aborning of Fischer-Tropsch. Therefore, the present invention relates to have low-sulfur, height paraffin, the moderate unsaturated distillate blending of fuel raw material of excellent stability and the distillate fuel that contains these blending raw materials. Low-sulfur, height paraffin, moderate unsaturated distillate blending of fuel raw material can be concocted raw material with other and be mixed to get distillate fuel, or can not have other blending raw material, only be directly used in engine under optional condition that adds a small amount of additive and act as a fuel.
For the present invention, here will use to give a definition:
Term " unsaturated compound " refers to contain the hydro carbons of one or more pairs of keys or triple bond, and for example preferred virtue belongs to and/or the olefinic degree of functionality.
Term " alkene " refers to contain the unsaturated straight or branched hydrocarbon (namely olefine) of at least one two key.
Term " aromatic hydrocarbons " refers to have undersaturated ring-type and the planar hydrocarbons of the uninterrupted electron cloud that contains odd number B duplet.
" distillate fuel blending raw material " is that a kind of and other distillate fuel blending raw material are mixed to get the particularly raw material of diesel oil or jet fuel of distillate fuel, as regulation here. Blending raw material itself not necessarily meets the technical specification about corresponding fuel, but preferably, the blending feedstock composition of generation meets the technical specification of corresponding fuel. Jet fuel blending raw material and other jet fuel are concocted raw material and additive combination randomly, obtain jet fuel. Equally, diesel fuel blending raw material and other diesel fuel are concocted raw material and additive combination randomly, obtain diesel fuel.
" aromatics blending raw material " for a kind of content that contains more than or equal to 50 % by weight, preferably greater than or equal to 75 % by weight, most preferably more than or equal to the blending raw material of the aromatic hydrocarbons of 90 % by weight. If the pure aromatics product is as aromatics blending raw material, the analysis of arene content is unnecessary so. If aromatics blending raw material contains aromatic hydrocarbons and other hydro carbons, the ASTM D6550 of improved form (measuring the standard test method of content of olefin in gasoline with supercritical fluid chromatography (SFC)) can be used to measure aromatic hydrocarbons so. Aromatics blending raw material can be concocted with Fischer-Tropsch process distillate fuel blending raw material, in order to improve the arene content of Fischer-Tropsch process distillate fuel blending raw material. The example of aromatics blending raw material comprises commercially available pure aromatics (such as benzene, alkylbenzene etc.); The aromatic hydrocarbons that is made by traditional oil product; Transformed the aromatic hydrocarbons that makes etc. by transformable fischer-tropsch products.
Measure cetane index by ASTM D4737-96a (2001) standard test methods with quaternary equation calculated cetane index.
The tradition petroleum products comprises the product that obtains from crude oil.
" oil blending raw material " is a kind of blending raw material that contains traditional petroleum products.The vapor stream of top of the tower that oil blending raw material can be obtained by crude oil or the distillation of refining petroleum product and form as the residual fuel of the lingering section that can not vaporize.
" obtain " being meant by Fischer-Tropsch process described raw material, blending raw material or product come from Fischer-Tropsch process or a certain stage by Fischer-Tropsch process production.
" Fischer-Tropsch process distillate fuel blending raw material " is a kind of blending raw material that comes from Fischer-Tropsch process or produce with Fischer-Tropsch process in a certain stage.Fischer-Tropsch process distillate fuel blending raw material can mix with other distillate fuel blending raw material, obtains distillate fuel, particularly diesel oil fuel or rocket engine fuel.Blending raw material itself not necessarily meets the technical specification about corresponding fuel, but the blending feedstock composition that generates meets the technical specification about corresponding fuel.Fischer-Tropsch process distillate fuel blending raw material comprises Fischer-Tropsch diesel fuels blending of fuel raw material and Fischer-Tropsch process rocket engine fuel blending raw material.As above-mentioned, Fischer-Tropsch process distillate fuel blending raw material can be concocted raw material with other and mix, obtain distillate fuel, or Fischer-Tropsch process distillate fuel blending raw material can there be other blending raw material, only be directly used in engine under optional condition that adds a small amount of additive and acts as a fuel.
Distillate fuel is a kind of material that boiling point is the hydro carbons of about 60 to 1100 that contains.The concrete fuel that comprises petroleum naphtha, rocket engine fuel, diesel oil fuel, kerosene, aviation spirit, oil fuel and tempered oil thereof is in the broad scope of distillate fuel.
Diesel oil fuel is a kind of material that is applicable to diesel motor.Preferably, diesel oil fuel meets at least a in the following technical specification:
ASTM D975-" the standard technique specification of diesel fuel oil "
Europe level CEN 90
Japan fuel standard JIS K 2204
The U.S. weighs and measures national meeting (NCWM) fine-quality diesel oil fuel guide in 1997
The fine-quality diesel oil fuel guide (FQP-1A) that EMA is recommended
Diesel oil fuel can be made up of various blending raw material combination or single blending raw material, does not have other blending raw material, the only optional a small amount of additive that adds.
Rocket engine fuel is a kind of material that is applicable to aircraft turbine engine or other purposes.Preferably, rocket engine fuel meets at least a in the following technical specification:
·ASTM D1655，
·DEF STAN 91-91/3(DERD 2494)，TURBINE FUEL，AVIATION，
·KEROSENE TYPE，JET A-1，NATO CODE：F-35，
International Air Transport Assoiciation (IATA) aviation guide material, the 4th edition, in March, 2000
Rocket engine fuel can be made up of various blending raw material combination or single blending raw material, does not have other blending raw material, the only optional a small amount of additive that adds.
Fischer-Tropsch diesel fuels blending of fuel raw material is a kind of blending raw material that is applicable to diesel motor.Fischer-Tropsch diesel fuels blending of fuel raw material can be concocted raw material with other and mix, and obtains diesel oil fuel, or can not have other blending raw material, only use under the optional situation that adds a small amount of additive.
Fischer-Tropsch process rocket engine fuel blending raw material is a kind of blending raw material that is applicable to aircraft turbine engine or other purposes.Fischer-Tropsch process rocket engine fuel blending raw material can be concocted raw material with other and mix, obtains rocket engine fuel, or can not have other blending raw material, only use under the situation of optional adding a small amount of additive.
Height paraffin, moderate unsaturated distillate blending of fuel raw material are a kind of containing greater than 70 weight % alkane, preferred 80 weight % or more alkane, most preferably 90 weight % or more alkane and 2-20 weight % unsaturated compound, preferred 2-15 weight % unsaturated compound, the distillate fuel blending raw material of 5-10 weight % unsaturated compound most preferably.Preferably, unsaturated compound not only comprises alkene but also comprise aromatic hydrocarbons, and most preferably the content of alkene is more than or equal to 1 weight %.Low-sulfur, height paraffin, moderate unsaturated distillate blending of fuel raw material contain the sulphur less than 1ppm.Preferably, height paraffin, moderate unsaturated distillate blending of fuel raw material are a kind of Fischer-Tropsch process distillate fuel blending raw material.
" raw material that Fischer-Tropsch process obtains " or " Fischer-Tropsch process raw material " is a kind of raw material Fischer-Tropsch process or that produce by Fischer-Tropsch process in a certain stage that comes from.In the method for the invention, in the course of processing, raw material that Fischer-Tropsch process can be obtained and the blending of oil blending raw material obtain a kind of blending logistics.
Synthetic gas is a kind of mixture that contains hydrogen and carbon monoxide.Except these thing classes, also can there be water, carbonic acid gas, unconverted light hydrocarbons raw material and various impurity.
" hydrocarbonaceous " or " hydro carbons " refers to contain the compound or the material of hydrogen atom and carbon atom, but it also can comprise heteroatoms for example oxygen, sulphur or nitrogen.
" peroxide precursor " refers to that those will form superoxide and/or cause the component that generates superoxide in hydrocarbon product in hydrocarbon product or charging.Peroxide precursor can be discerned, and the quantity of peroxide precursor can be stored in 60 ℃ of stoves by hydrocarbon product and be measured in 4 weeks.Peroxide precursor is discerned with the generation of superoxide, and the quantity of peroxide precursor can be measured on the basis that forms superoxide quantity.The method according to this invention, the peroxide level of sample is measured by the measurement superoxide cumulative program of using ASTM D3703 to describe.As an example, 4 ounces of samples are put into brown bottle and ventilated 3 minutes.After the testing period, test an aliquot sample by ASTM D3703 then, different is to replace freonll-11 with octane-iso.Test confirms, because environment reason, substituting of solvent do not have significantly influence to measuring result.The also available infrared spectra of the generation of superoxide, chemical method or measure by corroding elastomer sample.
The ASTM D6550 of modified version (measuring the standard test methods of the olefin(e) centent of gasoline with supercritical fluid chromatography (SFC)) is used to measure the type in raw material and the product.The method of improvement uses 3 point calibration standards to come the total amount of quantitative saturated compound, aromatic hydrocarbons, oxygenatedchemicals (polar compound) and alkene.With following compound calibration standard solution: undecane, toluene, n-Octanol and dodecylene.External standard method is used for quantitatively, and the limit of detection of aromatic hydrocarbons and oxygenatedchemicals is 0.1 weight %, and the limit of detection of alkene is 1.0 weight %.ASTM D6550 has described instrument condition.
The small part fuel sample is injected two placed in-line chromatographic column groups, carry as mobile phase with supercritical co.First chromatographic column is equipped with the high surface area silica particle.Second chromatographic column is equipped with Ag-bearing ionic high surface area silica particle.
Two switching valves are used for inhomogeneous component is sent into detector by the chromatogram system.In flow pattern forward, with saturated compound (normal alkane and branched paraffin and naphthenic hydrocarbon) by two chromatographic columns to detector, and alkene is captured on the chromatographic column of carrying silver, and aromatic hydrocarbons and oxygenatedchemicals are stayed on the silicon-dioxide chromatographic column.Aromatic hydroxy compound and oxygenatedchemicals are eluted to detector by the recoil mode subsequently from silica column.At last, alkene is sprung back over detector from the chromatographic column of carrying silver.
Flame ionization detector (FID) is used for quantitatively.Proofread and correct with respect to standard reference materials on the basis of the chromatographic signal area of saturated compound, aromatic hydrocarbons, oxygenatedchemicals and alkene, total saturated compound, aromatic hydrocarbons, oxygenatedchemicals and alkene that the latter is contained known quality % carry out overcorrection to density.The total mass of collecting is 100% ± 3%, normalizes to 100% for convenience's sake.
The polycyclic aromatic hydrocarbons of product (PNA) content is measured the diesel oil fuel and the aromaticity content of vaviation turbine fuel and the ASTM D5186-99 standard test methods of polycyclic aromatic hydrocarbon content with supercritical fluid chromatography and is measured.
The alkane content of product uses following algorithm to measure by supercritical fluid chromatography (SFC) analysis.SFC analyzes the observed value that aromatic hydrocarbons, alkene, oxygenatedchemicals and saturated compound are provided.Saturated compound in this analysis is the combination of alkane and naphthenic hydrocarbon (naphthene).Therefore,
Alkane=saturated compound (SFC)-naphthenic hydrocarbon
But, do not find in product of the present invention, to exist significant amounts naphthenic hydrocarbon (less than saturated compound 10%).Therefore, SFC analyzes the good and suitable observed value that the saturated compound that obtains can be used as the alkane content of product of the present invention usually.
In order to confirm do not have significant amounts naphthenic hydrocarbon to exist, measured the content of naphthenic hydrocarbon independently with GC-MS.GC-MS quotes alkene and naphthenic hydrocarbon sum, because they have identical hydrogen-carbon ratio in structure, described technology can not be distinguished them.If it is very little that GC-MS quotes the summation of alkene and naphthenic hydrocarbon, can draw naphthenic hydrocarbon so only has seldom amount existence.But, be significant if GC-MS quotes summation, the naphthenic hydrocarbon part can obtain naphthene content by deduct olefin(e) centent (measuring with SFC) from the GC-MS summation so.
Naphthenic hydrocarbon=(naphthenic hydrocarbon and alkene summation that GC-MS measures)-(alkene that SFC measures)
Naphthenic hydrocarbon can be deducted from saturated compound content (measuring with SFC) then, obtain the good and suitable observed value of alkane content according to the first party formula.If the naphthene content of measuring with this method is less than zero, so naphthene content just newspaper be zero, use separately in the calculating of alkane.Therefore, in this case, alkane is equivalent to the SFC saturated compound.
In the GC-MS test, deuterium-labelled standard substance is used for quantitative alkane, alkene, alcohols and acids.Selected deuterium-labeled compound is added in the sample of research as interior mark.With the mixture of trimethyl silyl (TMS) agent treated sample and standard substance, generate the TMS derivative, analyze with GCMS subsequently.Mass spectrograph is a Hewlett-Packard bench top mass spectrograph that is connected with HP GC with 60 meters non-polar columns.Normal paraffin and branched paraffin all use deuterium-labelled normal paraffin quantitative.Alkene, alcohols and acids all use corresponding deuterium-labeled compound quantitative.
The alkane content of the present invention height paraffin, the undersaturated blending raw material of moderate is at least 70 weight %, preferred 80 weight % or bigger, 90 weight % or bigger most preferably.Because high alkane content, the present invention's height paraffin, moderate unsaturated distillate blending of fuel raw material have fabulous combustionproperty.The feature combustionproperty that the present invention concocts raw material comprises that smoke point surpasses 25 millimeters, preferably surpasses 30 millimeters, and cetane index surpasses 60, preferably surpasses 65.Alkane is made up of the mixture of normal paraffin and isoparaffin, and the isoparaffin in fuel/normal paraffin is than being 0.3-10.When the blending raw material plans to use in harsh climate (the Jet A1 or the diesel oil that are used for the arctic), higher isoparaffin ratio is preferred.
The unsaturated compound content that the present invention concocts raw material is 2-20 weight %, preferred 2-15 weight %, 5-10 weight % most preferably.The unsaturated compound of blending raw material contains a small amount of polycyclic aromatic hydrocarbons.Preferably, unsaturated compound contain less than 25 weight % polycyclic aromatic hydrocarbonss, preferably less than 20 weight % polycyclic aromatic hydrocarbonss, be more preferably less than 10 weight % polycyclic aromatic hydrocarbonss even be more preferably less than 5 weight % polycyclic aromatic hydrocarbonss.Preferably, unsaturated compound not only contains alkene but also contain aromatic hydrocarbons, and most preferably, the content of alkene is more than or equal to 1 weight %.
The fuel that contains the present invention height paraffin, the undersaturated blending raw material of moderate preferably meets at least one technical specification about diesel oil fuel or rocket engine fuel.Fuel can be formed or not had other blending raw material, only formed under the situation of optional adding a small amount of additive by height paraffin, the undersaturated blending raw material of moderate by the blending raw material combination.Height paraffin, undersaturated blending raw material of moderate and the fuel that contains described blending raw material have acceptable stability at least, usually are fabulous stability.For example, the percentage reflectivity (as measuring down at 150 ℃) that contains the diesel oil fuel of height paraffin, the undersaturated blending raw material of moderate with ASTM D6468 surpass 65% (when measuring down) at 90 minutes, preferably surpass 65% (when measuring down) at 180 minutes, more preferably surpass 99% (when measuring down) at 180 minutes.The rocket engine fuel that contains height paraffin, the undersaturated blending raw material of moderate in ASTM D3241 (JFTOT program) acceptance value 260 ℃, 2.5 hours, preferably in ASTM D3241 (JFTOT program) acceptance value 270 ℃, 2.5 hours, more preferably in ASTM D3241 (JFTOT program) acceptance value at 300 ℃, 2.5 hours.Less than 3 (Code3), and the pressure drop by strainer is less than 25 mmhg corresponding to pipe rated value (tube rating) for acceptance value.
Blending raw material of the present invention and the fuel that contains described blending raw material have acceptable stability (according to traditional stability test) and acceptable anti-peroxidation rerum natura.Described blending raw material generates less than the 5ppm superoxide stored for 4 weeks in 60 ℃ of stoves after, preferably store in 60 ℃ of stoves and generate less than the 4ppm superoxide after 4 weeks, generate less than the 1ppm superoxide after more preferably storing for 4 weeks in 60 ℃ of stoves.Therefore, the blending raw material contains the peroxide precursor of such quantity, thus described fuel generate less than the 5ppm superoxide after in 60 ℃ of stoves, storing for 4 weeks, preferably in 60 ℃ of stoves, store generate less than the 4ppm superoxide after 4 weeks, more preferably in 60 ℃ of stoves, stored for 4 weeks after generations less than the 1ppm superoxide.By in 60 ℃ of stoves, storing the quantity of measuring peroxide precursor 4 weeks.The quantity of peroxide precursor can be measured on the basis of the superoxide quantity that generates.The available infrared spectra of the generation of superoxide, chemical method are measured, or measure by the erosion to elastomer sample.
Blending raw material of the present invention and the fuel that contains described blending raw material have usually low sulfur content (＜1ppm) and preferred low nitrogen content (＜1ppm).So the environmental emission of heteroatomic oxide compound is minimized.Therefore, described blending raw material and contain the fuel of described blending raw material because be eco-friendly but desirable.
Fischer-Tropsch process
Blending raw material of the present invention can be by the fischer-tropsch product by generating or keeping that hydroprocessing prepares under the condition of an amount of unsaturated compound.Preferably, blending raw material of the present invention to small part is obtained by Fischer-Tropsch process.
In the fischer-tropsch chemistry, synthetic gas changes into liquid hydrocarbon by contacting under reaction conditions with Fischer-Tropsch catalyst.Usually, can with methane and randomly more heavy hydrocarbons (ethane and more heavy hydrocarbon) make synthetic gas by traditional synthetic gas generator.Usually, synthetic gas contains hydrogen and carbon monoxide, also can contain amounts of carbon dioxide and/or water.The existence of sulphur, nitrogen, halogen, selenium, phosphorus and arsenic contamination thing is undesirable in synthetic gas.Owing to this reason and according to the quality of synthetic gas, preferably before carrying out the fischer-tropsch chemistry, from charging, remove desulfuration and other pollutent.For those skilled in the art, the method for removing these pollutents is that everybody is familiar with.For example, in order to remove sulphur impurity, ZnO protection bed is preferred.For those skilled in the art, the method for removing other pollutent is that everybody is familiar with.Also may wish purifying synthetic gas before the Fischer-Tropsch reaction device, remove the carbonic acid gas and any sulphur compound that other is not removed as yet that in the synthesis gas reaction process, generate.This point for example can contact in packing tower with weakly alkaline solution (for example wet chemical) by synthetic gas and realize.
In Fischer-Tropsch process, by containing H
2Under the temperature and pressure reaction conditions that is fit to, contact generation liquids and gases hydro carbons with the synthetic gas of CO mixture with Fischer-Tropsch catalyst.Usually, Fischer-Tropsch reaction can be carried out under the following conditions: about 300 to 700 of temperature (149-371 ℃), preferred about 400 to 550 (204-228 ℃); About 10 to 600psia (the 0.7-41 crust) of pressure, preferred 30-300psia (2-21 crust) and catalyzer air speed about 100 are to about 10,000 cubic centimetres/Grams Per Hour, preferred 300-3,000 cubic centimetre/Grams Per Hour.
Fischer-Tropsch process can be divided into high temperature Fischer-Tropsch process or low temperature Fischer-Tropsch process.The processing condition of two kinds of methods are different with primary product.
The high temperature Fischer-Tropsch process usually more than 250 ℃, preferably carry out more than 350 ℃ or 350 ℃.The high temperature Fischer-Tropsch process mainly obtains usually at C
3-C
8Lower molecular weight olefinic product in the scope, preferred propylene are to amylene.The high temperature Fischer-Tropsch process product also can contain a large amount of aromatic hydrocarbons.The high temperature Fischer-Tropsch process product can be handled and make aromatic hydrocarbons saturated, comprising reforming process.The olefinic product that the high temperature Fischer-Tropsch process obtains is further handled with oligomeric and hydrogenation step usually, generates high branch isoparaffin product.The product that the high temperature Fischer-Tropsch process obtains can be handled like this, so that they meet the technical specification of gasoline.The common cetane index of the product that the high temperature Fischer-Tropsch process obtains is about 55, because product is hyperbranched.The example of high temperature Fischer-Tropsch process is the Synthol method that SASOL uses, as what describe in " by the high yield high-quality diesel that Fischer-Tropsch process obtains, Dry, M.E., Chem.S.A., February 1984 ".
Rocket engine fuel is also produced with high temperature Fischer-Tropsch process, olefin oligomerization and hydrogenation.The high temperature Fischer-Tropsch process of producing rocket engine fuel is in " as the evaluation of the semi-synthetic Jet A-1 of the SASOL of commercial rocket engine fuel ", and SwRI-8531 describes among the November 1997.As what describe in the reference, with the rocket engine fuel aromatic free or the unsaturated compound of high temperature Fischer-Tropsch process production.The thermostability of the blending fuel of the rocket engine fuel that the rocket engine fuel that the high temperature Fischer-Tropsch process obtains and traditional oil obtain or JFTOT, breakthrough point are reported as in the document above 300 ℃.So the thermostability of so semi-synthetic tempered oil or JFTOT, breakthrough point are apparently higher than 260 ℃ of specification requirements.Referring to " as the evaluation of the semi-synthetic Jet A-1 of the SASOL of commercial rocket engine fuel ", Moses, Stavinoha, and Roets, South West ResearchInstitute Publication SwRI-8531, November 1997.
The researchist that the concoction of the component that high temperature Fischer-Tropsch process product and high temperature Fischer-Tropsch process product and oil are obtained is studied is stability problem not to be noted.
The low temperature Fischer-Tropsch process obtains heavier product in operation below 250 ℃.The heavier product of low temperature Fischer-Tropsch process mainly contains wax usually.The product that the low temperature Fischer-Tropsch process obtains is usually through hydrotreatment like this, so that they have acceptable peroxide stability, and as U.S. patent No.6,180,842 is disclosed.Therefore, the product of low temperature Fischer-Tropsch process is made with extra care with hydrotreatment operational example such as hydrotreatment and hydrocracking usually, so that obtain meeting the steady fuel of required technical specification.The product of low temperature Fischer-Tropsch process is mainly straight chain, even after hydrocracking, the product that these products obtain than high temperature Fischer-Tropsch process contains side chain still less.Have high side chain to compare with the product that the high temperature Fischer-Tropsch process obtains, in the product of low temperature Fischer-Tropsch process, less side chain provides higher cetane index for these products.The cetane index of low temperature fischer-tropsch product usually greater than 60, be preferably greater than 70.
The Fischer-Tropsch process of production distillate fuel blending of the present invention raw material is the low temperature Fischer-Tropsch process.For those skilled in the art, the condition of carrying out the reaction of low temperature fischer-tropsch type is that everybody is familiar with.
Product can be C
1-C
200+, main scope is C
5-C
100+Reaction can be carried out in various types of reactors, and the combination of fixed-bed reactor, slurry-phase reactor, fluidized-bed reactor or the dissimilar reactors of one or more beds is for example arranged.Such reaction process and reactor are that everybody is familiar with and describe in the literature.The slurries Fischer-Tropsch process is a kind of preferred method in the invention process, and its (mass transfer) characteristic of will well conducting heat is used for strong exothermic reaction, and can generate relative high-molecular weight paraffin-type when using cobalt catalyst.In slurry method, contain H
2With the synthetic gas of CO mixture as third phase by the slurry bubble in the reactor, described reactor contains and disperses and be suspended in the particulate state fischer-tropsch type hydrocarbon synthesis catalyst that contains under reaction conditions in the slurries of the building-up reactions hydrocarbon product of liquid.The mol ratio of hydrogen and carbon monoxide can change in about wide region of 0.5 to 4, changes but be more typically in about 0.7 to 2.75, preferred about 0.7 to 2.5 scope.
The Fischer-Tropsch catalyst that is suitable for contains one or more group VIII catalytic metals, for example Fe, Ni, Co, Ru and Re.In addition, the catalyzer of Shi Yonging also can contain promotor.Therefore, preferred Fischer-Tropsch catalyst contains the cobalt of effective quantity and one or more metals among Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and the La on the inorganic carrier material that is suitable for, described inorganic carrier material preferably comprises one or more infusible metal oxides.Usually, in the catalyzer content of cobalt be whole catalyst compositions about 1 to about 50 weight %.Catalyzer also can contain basic oxide promotor, for example ThO
2, La
2O
3, MgO and TiO
2, other promotor, for example ZrO
2, precious metal (Pt, Pd, Ru, Rh, Os, Ir), coinage metals (Cu, Ag, Au) and other transition metal, for example Fe, Mn, Ni and Re.Can use the solid support material that comprises aluminum oxide, silicon-dioxide, magnesium oxide and titanium dioxide or its mixture.For the catalyzer that contains cobalt, preferred carrier is a titanium dioxide.The Catalysts and its preparation method that is suitable for is known, and illustrative but nonrestrictive example for example can be at U.S. patent No.4, finds in 568,663.
More known catalyzer provide and are low to moderate medium chainpropagation possibility relatively, and reaction product comprises a high proportion of relatively lower molecular weight (C
2-8) alkene and the relative high molecular (C that hangs down ratio
30+) wax.More known other catalyzer provides high relatively chainpropagation possibility, and reaction product comprises the lower molecular weight (C of low relatively ratio
2-8) alkene and relative a high proportion of high molecular (C
30+) wax.For those skilled in the art, such catalyzer is that everybody is familiar with, and is easy to obtain and/or make.
The product that the low temperature Fischer-Tropsch reaction obtains comprises lightweight reaction product and wax reaction product usually.Wax reaction product (wax slop just) comprises the hydro carbons (for example vacuum gas oil is to heavy paraffin hydrocarbon) that about 600 of boiling point are above, and is most of at C
20+In the scope, be low to moderate C with the amount that reduces
10Lightweight reaction product and wax reaction product all are that alkane belongs to basically.Waxy product contains usually greater than 70% normal paraffin, usually greater than 80% normal paraffin.
Hydroprocessing
Usually, for those skilled in the art, hydroprocessing is that everybody is familiar with, and comprises the method that resembles hydrotreatment, hydrocracking, hydrogenation, the catalytic dewaxing or the combination of these methods.Preferably, hydroprocessing of the present invention most preferably reaches several purposes in single reaction vessel in one or several reactor.Wherein, the purpose of hydroprocessing has reduction or preferably removes heteroatoms for example nitrogen and sulphur fully.Though traditional hydroprocessing is removed unsaturated compound usually or obviously reduced its content, hydroprocessing of the present invention still keeps at least a portion unsaturated compound or produces aromatic hydrocarbons; Also generate the product that distillates with acceptable stability.And hydroprocessing can improve the isoparaffin/normal paraffin ratio that distillates in the product.In addition, hydroprocessing also can transform by the heavies class and improve the output that distillates product.At last, hydroprocessing also can carry out under the condition of generation or reservation moderate quatity unsaturated compound.
Hydroprocessing under the condition of generation or reservation unsaturated compound can reduce or eliminate the clean consumption of hydrogen in the hydroprocessing process.Though the adding of hydrogen needs for beginning hydroprocessing process, if the growing amount of aromatic hydrocarbons is enough high, the hydrogen amount of Chan Shenging can surpass the hydrogen amount that adds this process so in this course.Therefore, clean hydrogen output can be arranged from hydroprocessing of the present invention, just the clean consumption of hydrogen is less than 0.
The hydrogen of producing becomes in liquid (GTL) equipment to can be used for various uses in gas reforming.The hydrotreatment of various fischer-tropsch logistics is arranged, so that reduce or eliminate alkene and/or heteroatoms in these purposes.In addition, the hydrogen of production also can with the GTL process in produce or from containing CO
2Source of the gas in the CO that reclaims
2Reaction makes CO
2Reduce.CO
2-H
2The product that reaction obtains can be CO or fischer-tropsch product, and reaction can be carried out in synthetic gas generator.The hydrogen that generates also can be used as in fuel production and not generate CO
2The fuel element of discharge.The fuel of producing can be used for producing process heat, produces electric energy and/or distillation/purified water.
The Fischer-Tropsch process product hydroprocessing is 525-775 , preferred 575-725 with the representative temperature that keeps unsaturated compound or generation aromatic hydrocarbons.The typical pressure of this operation is less than 1000psig, preferably less than 600psig, 200-500psig most preferably.The typical liquid hourly space velocity (LHSV) of this operation was greater than 0.25 hour
-1, preferred 0.5-1.5 hour
-1The typical hydroprocessing catalyzer of this operation comprises catalyzer (hereinafter describing) that is used for traditional hydroprocessing or the catalyzer that is used for the hydroisomerization dewaxing, preferably, the combination that is used for the catalyzer of hydroprocessing and hydroisomerization dewaxing is cheaply as this combination, also can reduce the pour point of product simultaneously.
Traditional hydroprocessing catalyzer can be used for producing aromatic hydrocarbons and keeps unsaturated compound.The hydroprocessing catalyzer that is specially adapted to produce aromatic hydrocarbons is a dual-function catalyst, and they comprise hydrogenating function and acid function.The hydroprocessing catalyzer that generates aromatic hydrocarbons for example with traditional hydrotreating catalyst contrast, have acid function, because hydrotreating catalyst comprises for example aluminum oxide of non-acid carrier usually.
Acid function 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
5The mixture of metal oxide can prepare by such method, so that make at least a portion metal oxide high dispersing betwixt, for example SiO
2And Al
2O
3In the dispersion of atomic level, rather than SiO
2And Al
2O
3Discrete phase.SiO
2And Al
2O
3Discrete phase exist available XRD to check to measure.If all oxide compounds all exist mutually as discrete, the performance of catalyzer can descend so.The example of the acid function of being made up of mixed metal oxide is the SiO of zeolite, crystallization SAPO and codeposition
2-Al
2O
3
Though halogen can be used as acid function in the hydroprocessing catalyzer, particularly fluorochemical uses with the fluorided alumina form, and halogen is not preferred, because they can come out by slow stripping the device that can induce reaction corrosion from catalyzer.
Hydrogenating function in the hydroprocessing catalyzer of generation aromatic hydrocarbons comprises metal.The hydrogenation metal that is fit to comprises VI family metal for example Mo and/or W, and group VIII metal for example Ni or Co.They exist with the sulfurized form on catalyzer.Preferably, hydrogenation metal is a precious metal, more preferably is selected from Pt, Pd and composition thereof.They can be sulfurized, are preferred but use the unvulcanised form.
The catalyzer that is applicable to the hydroprocessing operation is that everybody is familiar with in this specialty.The catalyzer that is fit to comprises VIIIA family precious metal (according to international pure chemistry and applied chemistry association rule in 1975), for example load on platinum or palladium on aluminum oxide or the silicon matrix, and VIIIA and group vib metal, for example nickel-molybdenum on aluminum oxide or silicon matrix, cobalt-molybdenum, nickel-tungsten or nickel-Xi.When such compound when related special metal forms, base metal (for example nickel-molybdenum) hydrogenation metal exists as oxide compound in the final catalyst composition usually, or more preferably or may exist as sulfide.By the oxide compound of correspondence, preferred non-noble metal catalyst compositions contains and surpasses about 5 weight %, preferred about 5 to about 40 weight % molybdenum and/or tungsten, and at least about 0.5 weight %, usually about 1 to about 15 weight % nickel and/or cobalts.Precious metal (for example platinum) catalyzer can contain and surpass 0.01% metal, preferred 0.1-1.0% metal.Also can use the combination of precious metal, for example the mixture of platinum and palladium.
Matrix components comprises that some have the active matrix of acidic catalyst.One class has tart matrix to comprise soft silica-aluminum oxide or can be zeolite or the nonzeolite crystalline molecular sieve.The example of the substrate molecule sieve that is fit to comprises y-type zeolite, X type zeolite and so-called ultrastable Y and high structural silica dioxide: aluminum oxide compares y-type zeolite.The substrate material that is fit to also can comprise synthetic or natural substance and inorganic materials, for example carclazyte, silicon-dioxide and/or metal oxide for example silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silica-magnesia-zirconium white of silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania and ternary composition for example.The latter can be naturally occurring or is the form of gel precipitation or comprises silicon-dioxide and the gel form of the mixture of metal oxide.The carclazyte that can comprise polynite and kaolin families with the naturally occurring carclazyte of catalyst combination.Raw state when these carclazytes can originally be exploited is used, or passes through roasting, acid treatment or chemical modification at first.In reactor, can use more than one catalyst type.
As above-mentioned, usually for those skilled in the art, hydroprocessing is that everybody is familiar with, and it comprises the method that resembles hydrotreatment, hydrocracking, hydrogenation, the catalytic dewaxing or the combination of these methods.Hydroprocessing of the present invention is by carrying out the raw material that following operation comes the upgrading Fischer-Tropsch process to obtain, and described operation is selected from sulphur, nitrogen and the oxygen level that reduces in the raw material; Reduce the olefin(e) centent in the raw material; Isoparaffin in the product/normal paraffin ratio is brought up to 0.3-10; , the heavies class in the raw material improves the output of distillate fuel by being converted; And their combination.
Typical hydroprocessing condition changes in wide region.The typical pressure of this operation is less than 1000psig, preferably less than 600psig, 200-500psig most preferably.The typical liquid hourly space velocity (LHSV) of this operation was greater than 0.25 hour
-1, preferred 0.5-2.0 hour
-1The hydrogen cycle rate is usually greater than 50 standard cubic feet per barrel oil (SCF/Bbl), preferred 1000-5000SCF/Bbl.Temperature is that about 300 are to about 750 , preferred 450 -600 .
Hydrocracking can be undertaken by the known traditional method of those skilled in the art.Usually, hydrocracking is a kind of process that will bigger carbon-containing molecules be cracked into less carbon-containing molecules.It can contact in the presence of the hydrocracking catalyst that is fit to hydrogen under the following conditions by specific cut or cut combination carries out: temperature is about 600 to 900 (316-482 ℃), preferred 650-850 (343-454 ℃), pressure is about 200 to 4000psia (13-272 normal atmosphere), preferred 500-3000psia (34-204 normal atmosphere), is about 0.1 to 10 hour by the air speed of hydrocarbon raw material
-1, preferred 0.25 to 5 hour
-1Usually, the size of hydrocarbon molecules is reduced, make alkene key hydrogenation, make aromatic hydrogenation and remove micro-heteroatoms with hydrocracking.The suitable catalyzer of hydrocracking operation is known in this specialty, comprises the sulfurized catalyzer.The sulfurized catalyzer can contain soft silica-aluminum oxide, aluminum oxide, tungsten and nickel.
Hydroconversion condition industrial be that everybody is familiar with, comprise the temperature that is higher than envrionment temperature and be higher than atmospheric pressure.Preferred hydroconversion condition comprises temperature 300-800 , 400-600 most preferably, pressure 50-2000psig, 100-500psig most preferably, liquid hourly space velocity (LHSV) 0.2-10 hour
-1, most preferably 1.0-3.0 hour
-1, and gas velocity 500-10,000SCFB, 1000-5000SCFB most preferably.
The catalyzer that is used for hydrogenation is generally used for the catalyzer of hydrotreatment for those, but the unvulcanized catalyzer that contains Pt and/or Pd is preferred, preferably Pt and/or Pd is dispersed on the carrier, for example aluminum oxide, silicon-dioxide, silica-alumina or charcoal.Preferred carrier is a silica-alumina.
Catalytic dewaxing comprises Hydrodewaxing and the hydroisomerization dewax that two primary categories one are traditional; Hydroisomerization dewax is part hydroisomerization dewax and complete hydroisomerization dewax further.All categories all comprises the mixture of wax hydrocarbon stream and hydrogen is passed through containing on the catalyzer of acidic components, make in the charging normal paraffin and slightly the ramose isoparaffin change into the thing class of other non-wax, thereby obtain accepting the lube base raw material product of pour point (being lower than pact+10 or-12 ).The representative condition of all categories all comprised about 400 to 800 of temperature, pressure about 200 to 3000psig and air speed about 0.2 to 5 hour
-1The method that the charging dewaxing is selected for use depends on the wax content of quality product and charging usually, and traditional Hydrodewaxing is preferred for low wax content charging usually.The method of dewaxing can be selected to carry out by catalyzer.General theme is by Avilino Sequeira,
Lubricant Base Stock and Wax Processing, Marcel Dekker comments in the Inc 194-223 page or leaf.
At traditional Hydrodewaxing, partial hydrogenation isomerization dewaxing with fully in the hydroisomerization dewax, the decision of dewaxing catalyst classification can be made by using the n-hexadecane isomerization test, and is at U.S. patent No.5, disclosed in 282,958 as Santilli etc.When under 96% n-hexadecane transformation efficiency, measuring under the condition of descriptions such as Santilli, traditional catalyst for hydrogenation de-waxing will show the selectivity of generation isomerization n-Hexadecane less than 10%, the hydroisomerization dewax catalyzer will show the selectivity of generation isomerization n-Hexadecane more than or equal to 10%, the partial hydrogenation isomerization dewaxing catalyst will show the selectivity that generates the isomerization n-Hexadecane greater than 10% to less than 40%, and the hydroisomerization dewax catalyzer will show the selectivity of generation isomerization n-Hexadecane more than or equal to 40% fully, be preferably greater than 60%, most preferably greater than 80%.
For this file, traditional Hydrodewaxing is defined as using the catalytic dewaxing method of traditional catalyst for hydrogenation de-waxing.In traditional Hydrodewaxing, mainly be created on propane to the less alkane of ebullient between about octane by the cracking of wax molecular selectivity pour point is descended.Because this technology makes wax change into the lower by product of value, so it mainly is applicable to the oil product dewaxing that does not contain a large amount of waxes.Usually (Arabian, NorthSlope find in the petroleum distillate that etc) obtains this class wax oil product at medium wax crude oil.The catalyzer that is applicable to traditional Hydrodewaxing is generally 12-ring zeolite and 10-ring zeolite.This class zeolite comprises ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35 and mordenite.Compare with other alkane method for transformation, traditional catalyst for hydrogenation de-waxing helps cracking.This point confirms by the n-hexadecane isomerization test that uses Santilli etc., and wherein traditional catalyst for hydrogenation de-waxing shows and generates isomerization n-Hexadecane product selectivity less than 10%.Except zeolite, also metal can be added in the catalyzer, be mainly used in the minimizing fouling.The tradition Hydrodewaxing representative processes condition, productive rate and product property for example at U.S. patent Nos.4,176,050 (Chen etc.), 4,181,598 (Gillespie etc.), 4,222,855 (Pelrine etc.), 4,229, open among 282 (Peter etc.) and 4,211,635 (Chen).In all cases, these patents are here incorporated into as a reference.Processing condition are being entitled as " Mobile lubricating oil dewaxing method ", 198-204 page or leaf and reference thereof, J.D.Hargrove by Sequeira, G.J.Elkes and A.H.Richardson, Oil and Gas J., p.103, Jan.15,1979 part further describes and illustrates.
For this file, hydroisomerization dewax is defined as a kind of catalytic dewaxing method of using the hydroisomerization dewax catalyzer.Hydroisomerization dewax changes into the isoparaffin of non-wax with at least a portion wax by isomerization, minimizes and cracking is transformed.When traditional Hydrodewaxing and hydroisomerization dewax on the same feedstock basis relatively the time, in the hydroisomerization dewax process, the isoparaffin that wax changes into non-wax be reduced the productive rate that is worth low by product, improve lube oil yield and generate the benefit of the oil product of higher VI and bigger oxidative stability and thermostability.Hydroisomerization dewax uses the dual-function catalyst of being made up of acidic components and metal component.In order to carry out isomerization reaction, these two kinds of components all need.Typical metal component is platinum or palladium, the most normal use platinum.The selection of metal and quantity are to be enough to reach the isomerization n-Hexadecane product that has in the test of descriptions such as Santilli greater than 10% in the catalyzer.When the n-Hexadecane isomer selectivity according to the Santilli test surpassed 40%, catalyzer was complete hydroisomerization dewax catalyzer.Because hydroisomerization dewax makes wax change into ebullient isoparaffin in the lube basestocks scope, so it is applicable to the oil product dewaxing that contains a large amount of waxes.The overhead product that this class wax oil product derives from the slack wax that obtained by solvent dewaxing process, obtained by high wax crude oil (Minas, Altamont, etc.) and the product that obtains by Fischer-Tropsch process.
For this file, the partial hydrogenation isomerization dewaxing is defined as a kind of catalytic dewaxing method of using the partial hydrogenation isomerization dewaxing catalyst.In the partial hydrogenation isomerization dewaxing, use can make the isomerized catalyzer of alkane selectivity that a part of wax is isomerizated into isoparaffin, remains to low relatively numerical value (being usually less than 70%) but unique condition is a transformation efficiency with wax.Under higher conversion transformation efficiency, the cracking of wax transforms and becomes obviously, and the loss of yield of lube basestocks becomes uneconomical.An acidic catalyst component that is applicable to the partial hydrogenation isomerization dewaxing comprises soft silica-aluminum oxide, fluorizated aluminum oxide and 12-ring zeolite (for example β zeolite, y-type zeolite, zeolite L).Because the conversion of wax is incomplete,, be generally solvent dewaxing so the partial hydrogenation isomerization dewaxing must be aided with other DEWAXING TECHNIQUE.The wax that is reclaimed by the solvent dewaxing operation behind the partial hydrogenation isomerization dewaxing is capable of circulation to partial hydrogenation isomerization dewaxing step.
Representative processes condition, productive rate and the product property of partial hydrogenation isomerization dewaxing is for example at U.S. patent Nos.5, and be open among 049,536 (Belussi etc.) and 4,943,672 (Hamner etc.).In all cases, these patents are here incorporated into as a reference.Processing condition are further described in EP 0 582 347 (Perego etc.), EP 0 668 342 (Eilers etc.), PCT WO96/26993 (Apelian etc.) and PCT WO 96/13563 (Apelian etc.) and are illustrated.
For this file, hydroisomerization dewax is defined as a kind of catalytic dewaxing method of using complete hydroisomerization dewax catalyzer fully.In complete hydroisomerization dewax, use can make wax reach the complete hydroisomerization dewax catalyzer of high level of conversion, keeps acceptable isomerization selectivity simultaneously.An acidic catalyst component that is applicable to the partial hydrogenation isomerization dewaxing comprises 10-ring, 1 dimension molecular sieve (for example ZSM-23, SSZ-32, θ-1, ZSM-22, SAPO-11 and SAPO-41).Because the conversion of wax can be completely or at least very high, so in order to produce the lube basestocks that can accept pour point, this method does not need usually in conjunction with other DEWAXING TECHNIQUE.Representative processes condition, productive rate and the product property of hydroisomerization dewax are for example at U.S. patent Nos.5 fully, 135,638 (Miller etc.), U.S. patent Nos.5,246,566 (Miller etc.), U.S. patent Nos.5,282,958 (Santilli etc.), U.S. patent Nos.5,082,986 (Miller etc.) and U.S. patent Nos.5, open among 723,716 (Brandes etc.); In all cases, the content of each patent is here all incorporated into as a reference in these patents.
| Catalytic dewaxing | |||
| The tradition Hydrodewaxing | Hydroisomerization dewax | ||
| The partial hydrogenation isomerization dewaxing | Complete hydroisomerization dewax | ||
| Temperature, | 400-800 | ||
| Pressure, psig | 200-3000 | ||
| LHSV, hour -1 | 0.2-5.0 | ||
| N-C under 96% transformation efficiency 16Generate the selectivity of isomerized products | ＜10 | 10-40 | ＞40＞60 is preferred, and＞80 most preferably |
| Typical acidic components | ZSM-5, ZSM-11, ZSM-22, ZSM-35, mordenite | Silica-alumina, fluorizated aluminum oxide, β zeolite, y-type zeolite and zeolite L | ZSM-23, SSZ-32, θ-1, ZSM-22, SAPO-11 and SAPO-41 |
| Typical metal component | Choose wantonly, usually do not have | Pt or Pd, preferred Pt | Pt or Pd, preferred Pt |
With the blending of oil blending raw material
Distillate fuel of the present invention can be made up of the blending feedstock composition; Or distillate fuel can be made up of Fischer-Tropsch process distillate fuel blending raw material, do not have other blending raw material, only optional adding a small amount of additive.Therefore, distillate fuel can comprise and oil blending raw material blended Fischer-Tropsch process distillate fuel blending raw material.In the blending raw mix, preferred distillate fuel contains 1-95 weight % Fischer-Tropsch process blending raw material and 5-99 weight % oil blending raw material.More preferably, distillate fuel contains 5-75 weight % Fischer-Tropsch process blending raw material and 25-95 weight % oil blending raw material.Even more preferably, distillate fuel contains 10-50 weight % Fischer-Tropsch process blending raw material and 90-50 weight % oil blending raw material.
In addition, in the method for producing height paraffin, the undersaturated blending raw material of moderate, the Fischer-Tropsch process raw material can be concocted with oil blending raw material in any stage of this method, as long as obtain height paraffin of the present invention, moderate unsaturated distillate blending of fuel raw material.As an example, oil blending raw material can hydroprocessing before, after the hydroprocessing but removing before the polycyclic aromatic hydrocarbons or removing polycyclic aromatic hydrocarbons after but as before the distillate fuel and the raw material that obtains of Fischer-Tropsch process concoct.Preferably, oil blending raw material was concocted the blending logistics hydroprocessing that will generate then with the Fischer-Tropsch process raw material before hydroprocessing.If the Fischer-Tropsch process raw material mixes with oil blending raw material, preferably, the concoction of generation contains 1-95 weight % Fischer-Tropsch process raw material and 99-5 weight % oil blending raw material.More preferably, concoction contains 5-75 weight % Fischer-Tropsch process raw material and 95-25 weight % oil blending raw material.Even more preferably, concoction contains 10-50 weight % Fischer-Tropsch process raw material and 50-90 weight % oil blending raw material.
Remove polycyclic aromatic hydrocarbons
In order to satisfy the required low levels of polycyclic aromatic hydrocarbons in height paraffin, the undersaturated blending raw material of moderate, the product stream that hydroprocessing obtains can be through further processing, so that remove polycyclic aromatic hydrocarbons.Selectivity is removed the selection scheme that polycyclic aromatic hydrocarbons stays desirable mononuclear aromatics simultaneously and is comprised that selective hydrogenation is handled and absorption from product stream.
Remove from product stream that polycyclic aromatic hydrocarbons is most preferred to be operating as selective hydrogenation and to handle.The reaction conditions that selective hydrogenation is handled and the reaction conditions of above-mentioned hydrotreatment do not have big difference.The reaction conditions that selective hydrogenation is handled comprise low temperature (less than 750 , preferably less than 700 , most preferably less than 600 ), (LHSV was less than 5 hours for high pressure (greater than 250psig, be preferably greater than 350psig, most preferably greater than 500psig) and short contacting time
-1, preferably less than 3 hours
-1, most preferably less than 2 hours
-1).The preferred catalyst that is used for this selective hydrogenation processing contains Pt, Pd and combination thereof.The content to make polycyclic aromatic hydrocarbons descend at least 50 weight %, preferably at least 75 weight %, at least 90 weight % are most preferably handled in selective hydrogenation, and unsaturated compound content descend less than 50 weight %, preferably less than 35 weight %, most preferably less than 20 weight %.
From product stream, remove polycyclic aromatic hydrocarbons also can by at oxide carrier, preferably have moderate tart oxide carrier (acidic white earth is polynite or attapulgite for example) and adsorb and reach.The temperature of absorption should be less than 200 , preferably less than 150 .Also useable solvents extraction of polycyclic aromatic hydrocarbons, for example n-methyl-2-pyrrolidone, phenol or furfural.
Additive
Described distillate fuel and distillate fuel blending raw material can comprise the additive that is usually used in diesel oil or rocket engine fuel.The ChevronCorporation that is described in that can be used for diesel fuel additive of the present invention, Technical Review Diesel Fuels, describe among the pp.55-64 (2000), and can be used for the ChevronCorporation that is described in of additives for jet fuel of the present invention, describe among the Technical Review Aviation Fuels, pp.27-30 (2000).Particularly, these additives can include but not limited to antioxidant, oiliness additive, pour point reducer etc.A small amount of additive is added in fuel and the blending raw material, preferably less than 1 weight %.
Illustrative embodiment
Accompanying drawing is represented a kind of method for preparing height paraffin of the present invention, moderate unsaturated distillate blending of fuel raw material.With reference to figure 1, raw material (10) hydroprocessing in being added with the hydroprocessing unit (100) of hydrogen (20) that the low temperature Fischer-Tropsch process is obtained.The hydroprocessing condition comprise temperature 600-750 , pressure less than 1000psig and liquid hourly space velocity greater than 0.25 hour
-1The product of hydroprocessing (30) is a kind of height paraffin, moderate unsaturated distillate blending of fuel raw material, described height paraffin, moderate unsaturated distillate blending of fuel raw material contain 2-20 weight % unsaturated compound, and content makes that generation is less than the peroxide precursor of 5ppm superoxide after storing for 4 weeks under 60 ℃.Hydroprocessing can be produced hydrogen (60), and the latter can be used for other process, for example hydrotreatment, CO
2Reduction and fuel production.Optional is, height paraffin, moderate unsaturated distillate blending of fuel raw material (30) can be treated, removes polycyclic aromatic hydrocarbons (70) in operating unit (200).
Provide following examples and be used for illustrating the present invention, should be with they restrictions as the scope of the invention.
Embodiment
Embodiment 1
Light low temp f-t synthetic wax (Table I) is gone up LHSV 1 hour at sulfurized nickel-tungsten/silicon dioxide-aluminium oxide catalyst (a kind of traditional hydroprocessing catalyzer)
-1, hydrocracking under 1000psig, 685 and the 6.3MSCF/bbl.Under these conditions, the following transformation efficiency of 650 is 80.4 weight %.With product liquid fractionation under about 350 and about 675 , obtain the diesel oil blending feedstock fraction.The productive rate and the character of diesel oil blending raw material are listed Table II in.
Table I
The ingredient inspection of lightweight FT wax
| Proportion, API | 42.5 |
| Nitrogen, ppm | 3.2 |
| Sim.Dist.，LV％， | |
| ST/5 | 728/771 |
| 10/30 | 789/811 |
| 50 | 839 |
| 70/90 | 858/885 |
| 95/EP | 898/943 |
Table II
Lightweight FT wax is at Ni-W-SiO
2-Al
2O
3Go up LHSV 1 hour
-1, hydrocracking under 685 , 1000psig and the 6.3MSCF/BBL
| ＜650 transformation efficiencys, weight % | 80.4 |
| Productive rate, weight % | |
| C 1-C 2 | 0.03 |
| C 3-C 4 | 5.06 |
| C 5-180 | 17.77 |
| 180-350 | 20.85 |
| 350-650 | 37.51 |
| 650+ | 19.71 |
| C 5+ | 95.49 |
| 350-675 character | |
| The weight % of charging | 52.9 |
| Proportion, API | 50.7 |
| Viscosity, 40 ℃, cSt | 2.631 |
| Cloud point, ℃ | -26 |
| SFC analyzes, weight % | |
| Aromatic hydrocarbons | 0.3 |
| Alkene | 0.8 |
| Oxygenatedchemicals | ＜0.1 |
| Saturated compound | 98.9 |
| PNA aromatic hydrocarbons, weight % | Do not detect |
| Cetane index | 75.9 |
| Fan Shezhishuo @20 ℃ | 1.4342 |
| Density, g/ml @20 ℃ | 0.7745 |
| Molecular weight | 253 |
| The carbon type of ndM, weight %P/N/ | 100/0/0 |
| D2887Dist., weight %, | |
| ST/5 | 288/342 |
| 10/30 | 368/448 |
| 50 | 523 |
| 70/90 | 594/673 |
| 95/EP | 697/743 |
Detect the following 0.5 weight % that is limited to of PNA with supercritical fluid chromatography (SFC).Therefore, nd numerical value is less than this quantity.Because the high pressure traditional operation, operation only generates 0.3% aromatic hydrocarbons and keeps 0.8 weight % alkene under these conditions.The alkane content of this sample equals saturated compound content (98.9).The ndM analysis revealed that is applicable to the sample that contains non-olefinic does not have the naphthenic carbon structure.
Embodiment 2
Identical charging is in the identical catalyzer hydrocracking on the 3/1 multilayer bed of the sulfurized on the Pt/SAPO-11 catalyzer of embodiment 1 among the embodiment 1, and described Pt/SAPO-11 catalyzer is bonding with 15 weight % aluminum oxide.The Pt/SAPO-11 catalyzer is a kind of complete hydroisomerization dewax catalyzer.Identical among condition and the embodiment 3, it is total LHSV 1.0 hours
-1, 1000psig, 685 and 6.3MSCF/bbl H
2The transformation efficiency that is lower than 650 is 74.6 weight %.With product fractionation under about 350 and about 650 , obtain the diesel oil blending feedstock fraction.Productive rate and diesel oil blending raw material properties are listed Table III in.Measure as ASTM D6468, the diesel oil blending raw material is very stable.Because traditional high top pressure operation and Pt are as catalytic metal, the aromatic hydrocarbons in the diesel oil blending raw material is 0.1 weight %, and alkene is 0.3 weight %.Alkane content is 99.6, because do not have naphthenic hydrocarbon with GC-MS mensuration, and obtains the support that ndM analyzes.Cetane index very high (73.8) and cloud point very low (57 ℃).
Table III
Lightweight FT wax is at 3/1 NI-W-SIO
2-AL
2O
3/ PT-SAPO-11 is last LHSV 1 hour
-1, 685 , hydrocracking under 1000psig and the 6.3MSCF/BBL
| ＜650 transformation efficiencys, weight % | 74.6 |
| Productive rate, weight % | |
| C 1-C 2 | 0.08 |
| C 3-C 4 | 5.16 |
| C 5-180 | 13.02 |
| 180-350 | 15.70 |
| 350-650 | 40.97 |
| 650+ | 25.59 |
| C 5+ | 95.36 |
| 350-675 character | |
| The weight % of charging | 43.1 |
| Proportion, API | 51.3 |
| Viscosity, 40 ℃, cSt | 2.206 |
| Cloud point, ℃ | -57 |
| Alkene+naphthenic hydrocarbon, weight % (GC-MS) | Do not detect |
| PNA aromatic hydrocarbons, weight % | Do not detect |
| SFC analyzes, weight % | |
| Aromatic hydrocarbons | 0.1 |
| Alkene | 0.3 |
| Oxygenatedchemicals | ＜0.1 |
| Saturated compound | 99.6 |
| The % reflectivity, @150 ℃ of ASTM D6468 | |
| 1.5 hour | 99.7 |
| 3.0 hour | 99.8 |
| Cetane index | 73.8 |
| Fan Shezhishuo @20 ℃ | 1.4318 |
| Density, g/ml @20 ℃ | 0.7699 |
| Molecular weight | 239 |
| D2887 Dist., weight %, | |
| ST/5 | 314/352 |
| 10/30 | 370/433 |
| 50 | 496 |
| 70/90 | 549/606 |
| 95/EP | 629/676 |
Embodiment 3
Repeat embodiment 2, the stagnation pressure of different is reactor is 500psig, and temperature of reactor is 680 .The transformation efficiency that is lower than 650 is 63.5 weight %.With product fractionation under about 350 and about 590 , obtain the diesel oil blending feedstock fraction.Productive rate and diesel oil blending raw material properties are listed Table IV in.Measure as ASTM D6468, the diesel oil blending raw material is very stable.Aromatic hydrocarbons in the diesel oil blending raw material is 2.3 weight %.Cetane index still quite high (69.1) and cloud point very low (50 ℃).
Table IV
Lightweight FT wax is at 3/1 NI-W-SIO
2-AL
2O
3/ PT-SAPO-11 is last LHSV 1 hour
-1, 680 , hydrocracking under 500PSIG and the 6.3MSCF/BBL
| ＜650 transformation efficiencys, weight % | 63.5 |
| Productive rate, weight % | |
| C 1-C 2 | 0.23 |
| C 3-C 4 | 10.53 |
| C 5-180 | 13.98 |
| 180-350 | 15.63 |
| 350-650 | 23.72 |
| 650+ | 36.75 |
| C 5+ | 90.0 |
| 350-590 character | |
| The weight % of charging | 19.1 |
| Proportion, API | 51.1 |
| Viscosity, 40 ℃, cSt | 1.94 |
| Cloud point, ℃ | -50 |
| PNA aromatic hydrocarbons, weight % | Do not detect |
| The % reflectivity, @150 ℃ of ASTM D6468 | |
| 1.5 hour | 99.7 |
| 3.0 hour | 99.7 |
| Cetane index | 69.1 |
| Fan Shezhishuo @20 ℃ | 1.4323 |
| Density, g/ml @20 ℃ | 0.7704 |
| Molecular weight | 224 |
| D2887 Dist., weight %, | |
| ST/5 | 316/350 |
| 10/30 | 366/415 |
| 50 | 468 |
| 70/90 | 519/572 |
| 95/EP | 591/643 |
Embodiment 4
Low temperature f-t synthetic wax (Table V) hydrocracking on embodiment 2 identical multilayer bed catalyst systems with 700-1000 hydrotreatment.Condition comprises total LHSV 1.0 hours
-1, reactor pressure 300psig, top catalyzer 680 and bottom catalyzer 690 and 6.3MSCF/bbl H
2The transformation efficiency that is lower than 650 is 58.2 weight %.With product fractionation under about 300 and about 650 , obtain the diesel oil blending feedstock fraction.The productive rate of this product and diesel oil blending feedstock property are listed Table VI in.Measure as ASTM D6468, the diesel oil blending raw material is very stable.Aromatic hydrocarbons in the diesel oil blending raw material is 4.3 weight, and alkene is that 1.0 weight % and oxygenatedchemicals are 0.5 weight %.Alkane is equivalent to saturated compound (94.2%), because the GC-MS technology does not determine the alkene and the naphthenic hydrocarbon sum of significant amounts.Cetane index height (67.6) and cloud point is-44 ℃.
Table V
The ingredient inspection of the FT wax of 700-1000 hydrotreatment
| Proportion, API | 42.3 |
| Sim.Dist.，LV％， | |
| ST/5 | 691/804 |
| 10/30 | 824/884 |
| 50 | 919 |
| 70/90 | 940/974 |
| 95/EP | 991/1031 |
Table VI
The FT wax of 700-1000 hydrotreatment is at 3/1 NI-W-SIO
2-AL
2O
3/ Pt-SAPO-11 is last LHSV 1 hour
-1, the hydrocracking under 680 /690 , 300 PSIG and the 6.3MSCF/BBL
| ＜650 transformation efficiencys, weight % | 58.2 |
| Productive rate, weight % | |
| C 1-C 2 | 0 |
| C 3-C 4 | 4.78 |
| C 5-180 | 14.93 |
| 180-350 | 15.53 |
| 350-650 | 23.22 |
| 650+ | 41.92 |
| C 5+ | 95.7 |
| 350-650 character | |
| The weight % of charging | 31.1 |
| Proportion, API | 50.1 |
| Viscosity, 40 ℃, cSt | 2.027 |
| Cloud point, ℃ | -44 |
| Naphthenic hydrocarbon+alkene, weight % (GC-MS) | Do not detect |
| SFC analyzes, weight % | |
| Aromatic hydrocarbons | 4.3 |
| Alkene | 1.0 |
| Oxygenatedchemicals | 0.5 |
| Saturated compound | 94.2 |
| PNA aromatic hydrocarbons, weight % | 0.5 |
| The % reflectivity, @150 ℃ of ASTM D6468 | |
| 1.5 hour | 99.2 |
| 3.0 hour | 99.2 |
| Cetane index | 67.6 |
| Fan Shezhishuo @20 ℃ | 1.4348 |
| Density, g/ml @20 ℃ | 0.7741 |
| Molecular weight | 196 |
| The carbon type of ndM, weight %P/N/A | 92.40/5.01/2.59 |
| D2887 Dist., weight %, | |
| ST/5 | 266/300 |
| 10/30 | 325/396 |
| 50 | 472 |
| 70/90 | 561/645 |
| 95/EP | 667/698 |
Diesel oil blending raw material as embodiment 2 and 3, the diesel oil blending raw material of embodiment 4 shows fabulous stability, descends measurement to show in 180 minutes as ASTM D6468 at 150 ℃, the result surpasses 99%.The polycyclic aromatic hydrocarbon content of the diesel oil blending raw material of embodiment 4 is the 10 weight %s of 0.5 weight %-less than total unsaturated compound (5.3%).
Embodiment 5
Low temperature f-t synthetic wax and low temperature Fischer-Tropsch process lightweight condensation product (Table VII) are handled on traditional hydroprocessing catalyzer.168 centimetres
3/ hour wax and circulating liquid at 126 centimetres
3The acid amorphous Si O of sulfuration NiW/
2-Al
2O
3Hydrocracking on the catalyzer.With 106 centimetres
3/ hour the lightweight condensation product mix with the hydrocracking reactor effluent, then with mixture at 68 centimetres
3Sulfuration NiMo/ non-acidic alumina catalyzer on hydrotreatment.With the distillation of hydrotreating reactor effluent, obtain gas, petroleum naphtha, distillate fuel blending raw material and circulating liquid.Operational condition, productive rate and product characteristics are listed Table VIII in.Hydrocracking reactor is called Rx 1, and hydrotreating reactor is called Rx 2.
The character of Table VII Fischer-Tropsch process charging
| F-t synthetic wax | Fischer-Tropsch process lightweight condensation product | F-t synthetic wax | |
| The embodiment charging | 5 | 5 | 6 |
| Proportion, ° API | 40.3 | 53.5 | |
| Nitrogen, ppm | 1.27 | 2.36 | ＜0.25 |
| D2887 Dist., weight %, | |||
| ST/5 | 451/573 | 91/206 | 441/545 |
| 10/30 | 623/725 | 253/345 | 587/694 |
| 50 | 790 | 434 | 786 |
| 70/90 | 870/973 | 519/625 | 880/1009 |
| 95/EP | 1010/1068 | 651/702 | 1065/1161 |
Embodiment 6
228 centimetres
3/ hour the low temperature f-t synthetic wax (Table VII) of hydrotreatment at 300 centimetres
3The acid amorphous Si O of sulfurized NiW/
2-Al
2O
3In reactor 1 (Rx 1), handle on the catalyzer, and the effluent that merges centimetre
3The Pt/SAPO-11 catalyzer in reactor 2 (Rx 2), handle.Pt/SAPO-11 is bonding with 15 weight % aluminum oxide.The Pt/SAPO-11 catalyzer is a kind of complete hydroisomerization dewax catalyzer.The product distillation is obtained the diesel oil blending feedstock fraction.Productive rate, operational condition and product characteristics are listed Table VIII in.
Table VIII
Diesel oil and jet blending raw material properties under different pressures
| Embodiment | 15 | 15 | 15 | 15 | 16 |
| Pressure, psig | 1002 | 1002 | 297 | 297 | 298 |
| Rx 1/Rx 2 temperature, | 675/600 | 675/600 | 666/600 | 666/600 | 600/685 |
| Rx 1/Rx 2 LHSV | 1.3/4.0 | 1.3/4.0 | 1.3/4.0 | 1.3/4.0 | 0.76/2.3 |
| Recycle gas speed, SCFB | 5159 | 5159 | 4669 | 4669 | 4946 |
| Per pass conversion, LV% | 77.8 | 77.8 | 77.9 | 77.9 | - |
| The circulation cut point, | 702 | 702 | 696 | 696 | - |
| H 2Consume SCFB | 461 | 461 | 429 | 429 | 260 |
| The product boiling range, | 300-700 | 300-555 | 300-700 | 300-555 | 300-700 |
| Api gravity | 55.7 | 55.2 | 49.5 | ||
| Vis@，40℃，cSt | 2.055 | 2.237 | 2.817 | ||
| Cloud point, ℃ | 2 | 2 | -37 | ||
| N，ppm | ＜0.1 | ＜0.1 | ＜0.1 | 0.1 | ＜0.1 |
| S，ppm | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| SFC analyzes | |||||
| Aromatic hydrocarbons, quality % | 1.2 | 0.9 | 1.4 | ||
| Alkene, quality % | 5.4 | 4.8 | 2.6 | ||
| Oxygenatedchemicals, quality % | 0.2 | ＜0.1 | ＜0.1 | ||
| Saturated compound, quality % | 93.2 | 94.3 | 96.0 | ||
| @260 ℃ of JFTOT test | Qualified | Qualified | |||
| @300 ℃ of JFTOT test | Qualified | Qualified | |||
| @150 ℃ of D6468 stability | |||||
| 90 minutes | 99.3，99.6 | 99.8，99.7 | |||
| 180 minutes | 99.8，99.8 | 99.8.99.8 | |||
| The superoxide growing amount, ppm | |||||
| 0 week | 1 | 1 | ＜1 | ＜1 | |
| 1 week | ＜1 | 1 | ＜1 | ＜1 | |
| 2 weeks | ＜1 | 1 | ＜1 | ＜1 | |
| 3 weeks | ＜1 | 1 | ＜1 | ＜1 | |
| 4 weeks | 1 | 1.3 | 1 | ＜1 | |
| Acid number, milligram KOH/ gram | 0.06 | ＜0.05 | ＜0.05 | ||
| The D2887 distillation, weight %, | |||||
| 0.5/5 | 287/304 | 285/302 | 293/309 | 289/305 | 285/326 |
| 10/20 | 343/384 | 310/346 | 344/385 | 321/348 | 357/422 |
| 30/40 | 420/455 | 382/392 | 421/465 | 385/397 | 476/525 |
| 50 | 489 | 422 | 516 | 424 | 562 |
| 60/70 | 523/565 | 451/463 | 548/586 | 455/467 | 593/623 |
| 80/90 | 603/652 | 491/521 | 625/663 | 492/522 | 652/679 |
| 95/99.5 | 689/761 | 525/547 | 685/729 | 525/548 | 692/708 |
The product that makes under the 300psig contains greater than 2 weight % unsaturated compounds, greater than 1 weight % alkene, and the sulphur less than 1ppm is arranged, and also has fabulous stability and fabulous antiperoxide generative nature in diesel oil fuel and rocket engine fuel test.All products all have greater than 90% alkane.General existence owing to more activated Pt component, the product that is obtained by the Pt/SAPO-11 catalyzer shows lower olefin(e) centent.
Be a series of Comparative Examples below, illustrate that generating untreated Fischer-Tropsch process product with regard to superoxide is the product that unsettled and traditional hydroprocessing operation obtains extremely low quantity unsaturated compound, it is stable generating it with regard to superoxide.
The preparation of the diesel oil blending raw material of the complete hydrogenation of Comparative Examples 7-
By three kinds of low temperature Fischer-Tropsch process feedstock production height paraffin, diesel oil blending raw material.
Table I X-Fischer-Tropsch process raw material properties
| Character | Raw material 1 | Raw material 2 | Raw material 3 |
| Weight % in the concoction | 27.8 | 23.1 | 49.1 |
| Proportion, ° API | 56.8 | 44.9 | 40.0 |
| Sulphur, ppm | ＜1 | ＜1 | |
| Oxygen, ppm by Neut.Act. | 1.58 | 0.65 | |
| Chemical type, weight % measures with GC-MS | |||
| Alkane | 38.4 | 62.6 | 85.3 |
| Alkene | 49.5 | 28.2 | 1.6 |
| Alcohols | 11.5 | 7.3 | 9.3 |
| Other thing class | 0.5 | 3.9 | 3.8 |
| The D-2887 distillation, weight %, | |||
| 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 |
Different material is sent into the hydroprocessing reactor with downward stream mode prepare the blending raw material continuously.That reactor is equipped with is salic, the catalyzer of silicon-dioxide, nickel and tungsten.Catalyzer is before use through sulfuration.Make the per pass conversion below the cut point 665-710 be maintained at about 80% by regulating catalyst temperature.
After the separation and the unreacted hydrogen that circulates, the product of hydroprocessing reactor obtains gaseous by-product, light naphtha, diesel oil blending feedstock fraction and unconverted cut through continuous still battery.Unconverted cut is recycled to the hydroprocessing reactor.Regulate the temperature of distillation tower, make flash-point and cloud point remain on 58 ℃ of its target value and-18 ℃ respectively.
Under 1.4LHSV, raw material concocted constant operation a few hours, obtain the representative product A in the Table X.
The character of the distillate fuel blending raw material product of Table X-blending
| Sample ID | A | B | ||
| Proportion, ° API | 52.7 | 52.5 | ||
| Nitrogen, ppm | 0.24 | 0.25 | ||
| Sulphur, ppm | ＜1 | 0.61 | ||
| Water, ppm karl fischer method, ppm | 21.5 | |||
| Pour point, ℃ | -23 | -23 | ||
| Cloud point, ℃ | -18 | -18 | ||
| Flash-point, ℃ | 58 | 59 | ||
| Auto ignition temp, | 475 | 410 | ||
| 25 ℃ of viscosity, cSt | 2.564 | 2.304 | ||
| 40 ℃ of viscosity, cSt | 1.981 | 1.784 | ||
| Cetane value | 74 | 72.3 | ||
| The aromatic hydrocarbons that supercritical fluid chromatography is measured, weight % | ＜1 | 0.9 | ||
| In and No. | 0 | |||
| The ash sub-oxide, weight % | ＜0.001 | |||
| Ramsbottom coke, weight % | 0.02 | |||
| Copper corrosion | 1A | |||
| Color, ASTM D 1500 | 0 | 0.2 | ||
| GC-MS analyzes | ||||
| Alkane, weight % | 100 | 81.64 | ||
| Alkane isomery/positive structure ratio | 2.1 | 1.02 | ||
| As the oxygen of oxygenatedchemicals, ppm | ＜6 | 1226 | ||
| Alkene, weight % | 0 | 17.52 | ||
| Average carbon number | 14.4 | 13.20 | ||
| The D-2887 distillation, weight %, and D-86 distillation, volume %, | D-2887 | D-86 | D-2887 | D-86 |
| 0.5/5 | 255/300 | 329/356 | 256/298 | 334/360 |
| 10/20 | 326/368 | 366/393 | 329/367 | 366/-- |
| 30/40 | 406/449 | 419/449 | 400/429 | 413/-- |
| 50 | 487 | 480 | 463 | 466 |
| 60/70 | 523/562 | 510/539 | 500/537 | --/519 |
| 80/90 | 600/637 | 567/597 | 574/605 | --/572 |
| 95/99.5 | 659/705 | 615/630 | 626/663 | 587/604 |
Oxygen can the organic oxygen-containing compound form in sample (measuring with gas chromatography-mass spectrum (GC-MS)), the water (measuring with karl fischer method) of dissolved or suspension or dissolved O from air
2Exist.
Oxygenates level is measured with GC-MS.Oxygenatedchemicals in the sample is handled with tetraethoxy-silicane (TEOS), with the susceptibility that develops skill.Sample A does not detect oxygenatedchemicals.The limit of detection of this technology is confirmed as 6.5ppm according to oxygenatedchemicals.With regard to the molecular weight ranges of diesel oil fuel, this is equivalent to 0.6ppm oxygen (oxygenatedchemicals form).The 10 kinds of oxygenatedchemicalss of supposing to have an appointment in the typical sample just are lower than this limit of detection, and the oxygen maximum quantity of oxygenatedchemicals form is 6ppm (0.0006 weight %) in the sample so.
Use derives from O in the pure compound
2The data of solubleness, estimation derives from the O of air in product A
2Solubleness be about 92ppm (0.0092 weight %).There is not available measurement dissolving O
2Method.The GC-MS analytical results is listed Table X I in.
The GC-MS of Table X I-distillate fuel blending raw material analyzes
| Molecular formula | Normal paraffin, area % | Branched alkane, area % | Total alkane | Press the isomery/positive structure ratio of 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 |
| % alkane | 100.00 |
| % alkene | 0.00 |
| Average carbon number | 15.12 |
| The boiling point of average carbon number, | 521 |
| Gross sample alkane isomery/positive structure ratio | 2.08 |
As what point out above, in this product A, do not detect oxygenatedchemicals.In addition, product A contains less than 1 weight % aromatic hydrocarbons.The shortage of aromatic hydrocarbons further improves the possibility of product A with rapid oxidation.
Comparative Examples 8
The preparation of olefinic diesel oil fuel blending raw material
In this embodiment, the raw material 1 of the Fischer-Tropsch process product among the Table X I is walked around the hydroprocessing unit, and directly sends into distillation tower.Use same catalyst and the condition used among the embodiment 7, comprise that LHSV is 1.4, and the condition of adjusting distillation tower makes the flash-point of product and cloud point remain on the value of using among the embodiment 7.Because the final boiling point that needs to reduce diesel oil fuel blending raw material is to keep its cloud point, the productive rate of diesel oil fuel blending raw material is less, about 73%.
Diesel oil fuel is concocted raw material under constant operation, concoct a few hours, obtain the representative product B in the Table X.Send into the unitary operation of hydroprocessing with all fischer-tropsch logistics and compare, because lower diesel-fuel end point is walked around light component the productive rate of diesel oil fuel blending raw material is descended.Lower diesel-fuel end point may be the result of the heavy normal paraffin of higher concentration in the product B.The GC-MS analytical results of product B is listed Table X II in.
The GC-MS of Table X II-product B analyzes
| Carbon number | The 1-alkene | Normal paraffin | Isoparaffin | Alcohols | Add up to | Alkane isomery/positive structure 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 |
| Add up to | 17.52 | 40.32 | 41.14 | 1.02 | 100.00 |
| % alkane | 81.46 |
| % alkene | 17.52 |
| Average carbon number | 13.20 |
| The oxygen of oxygenatedchemicals form, ppm | 1226 |
| Gross sample alkane isomery/positive structure ratio | 1.02 |
These results also show, when a part of Fischer-Tropsch process product is walked around the hydroprocessing reactor and concoct in final blending raw material, comprise a large amount of alkene in blending raw material product.In fact, the alkene in blending raw material product is bigger 10 times than alcohols.Alkene and oxygenatedchemicals cause the potential stability problem.
Embodiment 9
Stability measurement
Press ASTM D6468 and tested product B 180 minutes down at 150 ℃, obtain 99.3% stability, this shows that it generates settling in this test is stabilizer pole.
Then according to U.S. patent Nos.6, disclosed method generates quickening to form the superoxide of having tested product under the superoxide in 162,956 and 6,180,842.Standard program according to the accumulation that is used to measure superoxide has been tested product.At first, 4 ounces of samples are put into brown bottle, and inflated 3 minutes.Test a part of sample according to ASTM D3703 then about superoxide.With the peroxide level of the program measure sample of following ASTM D3703, different is to replace the freonll-11 solvent with octane-iso.Sample is added a cover then, and puts for 1 week in 60 ℃ of stoves.After this repeat the superoxide number, sample is returned in the stove.This program continues weekly, always through 4 weeks, and obtains final superoxide number.Table X III comprises superoxide and generates trend.
Table X III-superoxide generates trend
| A | B | |
| The initial peroxide number | 1.3 | 8.2 |
| Superoxide number after 60 ℃ of following 1 weeks | 1.0 | 35 |
| Superoxide number after 60 ℃ of following 2 weeks | 1.5 | 156 |
| Superoxide number after 60 ℃ of following 3 weeks | 1.88 | 204 |
| Superoxide number after 60 ℃ of following 4 weeks | ＜5 | ＞5 |
Under 70 ℃, carried out another test of product A.Initial peroxide number and the superoxide number after 4 weeks are all less than 1ppm.These results show that the peroxide stability of product A is more much better than product B.These test-results illustrate the stability of low temperature Fischer-Tropsch process product of complete hydrogenation and the trend of very rapid generation superoxide that contains the distillate fuel blending raw material of the not fischer-tropsch logistics of hydroprocessing.
Trace alkene is to the influence of peroxide stability
Carried out another research, be added to the influence of the stable blending raw material product A of Table X so that determine a small amount of olefinic condensation product.Distillation makes the 300-600 part of the cold condensate of low temperature, the raw material 1 of Table I X.The character of the 300-600 part of this cold condensate is as follows:
The character of the 300-600 part of the cold condensate of Table X IV-
| Character | Numerical value |
| Api gravity | 65.3 |
| Nitrogen, ppm | 0.79 |
| Sulphur, ppm | 2.29 |
| Bromine No. | 48.2 |
| Simulation distil, D-2887 , weight % | |
| 0.5/5％ | 296/302 |
| 10/30％ | 332/382 |
| 50％ | 393 |
| 70/90％ | 459/523 |
| 95/99.5％ | 551/654 |
The GC-MS of the 300-600 part of cold condensate analyzes these results that obtain representing with weight %:
The GC-MS of the 300-600 part of the cold condensate of Table X V-analyzes
| Carbon number | Normal olefine | Alkane | Alcohols | Add up to |
| 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 20 | 0.06 | 0.21 | 0.00 | 0.26 |
| Add up to | 56.87 | 37.10 | 6.03 | 100.00 |
| % alkane | 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
The 300-600 part of cold condensate is estimated the generation of superoxide then with the steady fuel blending raw material A blending of different quantities and Table X to concoction, following result is arranged:
The superoxide of Table X VI-concoction 1-5 generates
| Sample No. | Cold condensate volume, milliliter | The steady fuel volume, milliliter | Alkene in the concoction, | 60 ℃ of superoxide results that store down after several weeks, ppm | ||||
| 0 | 1 | 2 | 3 | 4 | ||||
| 1 | 0 | 100 | 0 | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| 2 | 0.2 | 99.8 | 0.1 | ＜1 | ＜1 | ＜1 | 1.1 | 1.0 |
| 3 | 0.5 | 99.5 | 0.3 | ＜1 | ＜1 | 1.6 | 5.3 | 6.7 |
| 4 | 1 | 99.0 | 0.6 | 1.2 | 2.5 | 7.7 | 20.0 | 37.0 |
| 5 | 2 | 98.0 | 1.13 | 1.1 | 5.6 | 23.2 | 53.0 | 58.0 |
These results show that with regard to the generation of superoxide, the blending raw material that does not all have direct cold condensate blending to make by hydrotreatment is stable.The blending raw material only can allow up to the cold condensate of 0.2 weight % (oxygenatedchemicals and about 0.1 weight % alkene of the 0.012 weight % alcohol form of measuring with GC-MS), and still is considered to stable.The blending raw material that contains greater than 0.012 weight % oxygenatedchemicals or 0.1 weight % alkene does not have gratifying stability.Along with the content of oxygenatedchemicals surpasses 0.012 weight %, the peroxide stability of blending raw material descends rapidly.
Though described the present invention in detail with reference to specific embodiment, those skilled in the art will be appreciated that, can make various changes and improvements under the condition of spirit of the present invention and scope.
Claims (41)
1. one kind contains the distillate fuel that the Fischer-Tropsch process distillate fuel is concocted raw material, and wherein said Fischer-Tropsch process distillate fuel blending raw material comprises:
A) content is the unsaturated compound of 2-20 weight %;
B) content is 80 weight % or more alkane;
C) content is less than the sulphur of 1ppm;
D) cetane index is greater than 60; With
E) peroxide precursor, its content make 60 ℃ to store the back generation of 4 weeks down less than the 5ppm superoxide.
2. according to the distillate fuel of claim 1, wherein the quantity of peroxide precursor is such, so that generates less than the 4ppm superoxide after storing for 4 weeks under 60 ℃.
3. according to the distillate fuel of claim 1, wherein the quantity of peroxide precursor is such, so that generates less than the 1ppm superoxide after storing for 4 weeks under 60 ℃.
4. according to the distillate fuel of claim 1, the distillate fuel of wherein about 100 weight % is Fischer-Tropsch process distillate fuel blending raw material.
5. according to the distillate fuel of claim 1, it also comprises oil blending raw material.
6. according to the distillate fuel of claim 5, wherein this fuel contains 5-75 weight % Fischer-Tropsch process distillate fuel blending raw material and 95-25 weight % oil blending raw material.
7. according to the distillate fuel of claim 1, wherein distillate fuel also comprises the nitrogen of quantity less than 1ppm.
8. according to the distillate fuel of claim 1, wherein the quantity of unsaturated compound is 2-15 weight %.
9. according to the distillate fuel of claim 1, wherein the quantity of unsaturated compound is 5-10 weight %.
10. according to the distillate fuel of claim 1, wherein distillate fuel meets at least one technical specification about diesel oil fuel or rocket engine fuel.
11. according to the distillate fuel of claim 10, wherein distillate fuel meets at least one technical specification about diesel oil fuel, its cetane index is greater than 60.
12. according to the distillate fuel of claim 11, wherein the cetane index of distillate fuel is greater than 65.
13. according to the distillate fuel of claim 11, wherein when when measuring 90 minutes for 150 ℃, the ASTM D6468 percentage reflectivity of fuel surpasses 65%.
14. according to the distillate fuel of claim 11, wherein when when measuring 180 minutes for 150 ℃, the ASTM D6468 percentage reflectivity of fuel surpasses 65%.
15. according to the distillate fuel of claim 11, wherein when when measuring 180 minutes for 150 ℃, the ASTM D6468 percentage reflectivity of fuel surpasses 99%.
16. according to the distillate fuel of claim 10, wherein distillate fuel meets at least one technical specification about rocket engine fuel, acceptance value was at 260 ℃, 2.5 hours in ASTM D3241.
17. according to the distillate fuel of claim 16, wherein fuel in ASTM D3241 acceptance value at 270 ℃, 2.5 hours.
18. according to the distillate fuel of claim 16, wherein fuel in ASTM D3241 acceptance value at 300 ℃, 2.5 hours.
19. a Fischer-Tropsch diesel fuels blending of fuel raw material, it comprises:
A) content is the unsaturated compound of 2-10 weight %, and wherein unsaturated compound contains less than 10 weight % polycyclic aromatic hydrocarbonss;
B) content is 90 weight % or more alkane;
C) content is less than the sulphur of 1ppm; And
D) peroxide precursor, its content make 60 ℃ to store the back generation of 4 weeks down less than the 5ppm superoxide,
Wherein the cetane index of fuel is greater than 60; With when measuring 180 minutes, surpass 99% at 150 ℃ of following ASTM D6468 percentage reflectivity.
20. according to the blending raw material of claim 19, the cetane index of wherein concocting raw material is greater than 65.
21. according to the blending raw material of claim 19, the cetane index of wherein concocting raw material is greater than 70.
22. a Fischer-Tropsch process rocket engine fuel blending raw material, it comprises:
A) content is the unsaturated compound of 2-10 weight %, and wherein unsaturated compound contains less than 10 weight % polycyclic aromatic hydrocarbonss;
B) content is 90 weight % or more alkane;
C) content is less than the sulphur of 1ppm;
D) peroxide precursor, its content make 60 ℃ to store the back generation of 4 weeks down less than the 5ppm superoxide;
E) smoke point is 30 millimeters or bigger; And
F) in ASTM D3241 acceptance value at 260 ℃, 2.5 hours.
23. according to the blending raw material of claim 22, wherein concoct raw material in ASTM D3241 acceptance value at 270 ℃, 2.5 hours.
24. according to the blending raw material of claim 22, wherein concoct raw material in ASTM D3241 acceptance value at 300 ℃, 2.5 hours.
25. a method for preparing height paraffin, moderate unsaturated distillate blending of fuel raw material, it may further comprise the steps:
A) with Fischer-Tropsch process synthetic gas is changed into the raw material that Fischer-Tropsch process obtains;
B) raw material that described Fischer-Tropsch process is obtained at temperature 525-775, pressure less than 1000psig and liquid hourly space velocity greater than 0.25 hour-1 time hydroprocessing; With
C) reclaim height paraffin, moderate unsaturated distillate blending of fuel raw material, wherein said height paraffin, moderate unsaturated distillate blending of fuel raw material contain 2-20 weight % unsaturated compound, less than 1ppm sulphur and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide.
26. according to the method for claim 25, wherein temperature is 575-725 °F, pressure is that 200-500psig and liquid hourly space velocity are 0.5-1.5 hour-1.
27. according to the method for claim 25, the raw material upgrading that wherein said hydroprocessing obtains Fischer-Tropsch process by the operation that is selected from down group: the content that reduces sulphur, nitrogen and oxygen in the raw material; Reduce the content of alkene in the raw material; Isoparaffin in the product/normal paraffin ratio is brought up to 0.3-10; Be converted by heavies class in the raw material and improve distillate fuel product output; And combination.
28. according to the method for claim 25, wherein hydroprocessing is produced hydrogen, and reclaims the hydrogen of producing.
29. according to the method for claim 26, wherein hydroprocessing is produced hydrogen, and the hydrogen of producing is used to be selected from hydrotreatment, CO
2The process of reduction, fuel production and combination thereof.
30. according to the method for claim 25, wherein hydroprocessing takes place in the presence of the hydroprocessing catalyzer that uses acid carrier.
31. according to the method for claim 25, it also comprises from height paraffin, moderate unsaturated distillate blending of fuel raw material removes at least a portion polycyclic aromatic hydrocarbons.
32. according to the method for claim 25, it comprises also that raw material that Fischer-Tropsch process is obtained mixes with oil blending raw material and obtains a kind of blending logistics and described concoction stream is carried out hydroprocessing.
33. a distillate fuel that contains Fischer-Tropsch process distillate fuel blending raw material, wherein said Fischer-Tropsch process distillate fuel blending raw material is by a kind of like this method preparation, and this method comprises:
A) with Fischer-Tropsch process synthetic gas is changed into the raw material that Fischer-Tropsch process obtains;
B) raw material that described Fischer-Tropsch process is obtained at temperature 525-775, pressure less than 1000psig and liquid hourly space velocity greater than 0.25 hour-1 time hydroprocessing; And
C) reclaim Fischer-Tropsch process distillate fuel blending raw material, wherein said Fischer-Tropsch process distillate fuel blending raw material contain 2-20 weight % unsaturated compound, less than 1ppm sulphur and content make 60 ℃ store down 4 week the back generate peroxide precursor less than the 5ppm superoxide.
34. according to the distillate fuel of claim 33, wherein said fuel meets at least one technical specification about diesel oil fuel or rocket engine fuel.
35. according to the distillate fuel of claim 34, wherein said fuel meets at least one technical specification about diesel oil fuel, its cetane index is greater than 60.
36. according to the distillate fuel of claim 34, wherein said fuel meets at least one technical specification about diesel oil fuel, its cetane index is greater than 65.
37. according to the distillate fuel of claim 34, wherein said fuel meets at least one technical specifications about rocket engine fuel, and in ASTM D3241 acceptance value at 260 ℃, 2.5 hours.
38. comprising the Fischer-Tropsch process that uses claim 19, the method for an operating diesel engines, this method concoct raw material as diesel oil fuel.
39. according to the method for the operating diesel engines of claim 38, wherein diesel oil fuel also comprises oil blending raw material.
40. comprising the Fischer-Tropsch process that uses claim 22, a method of operating jet engine, this method concoct raw material as rocket engine fuel.
41. according to the method for the operation jet engine of claim 40, wherein rocket engine fuel also comprises oil blending raw material.
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| US10/464,635 | 2003-06-19 |
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-
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- 2003-06-19 US US10/464,635 patent/US20070187292A1/en not_active Abandoned
-
2004
- 2004-06-16 CN CNB2004800238847A patent/CN100465251C/en not_active Expired - Lifetime
- 2004-06-16 JP JP2006517325A patent/JP2007520579A/en active Pending
- 2004-06-16 AU AU2004252510A patent/AU2004252510B2/en not_active Ceased
- 2004-06-16 ZA ZA200600302A patent/ZA200600302B/en unknown
- 2004-06-16 WO PCT/US2004/019252 patent/WO2005001002A2/en active Application Filing
- 2004-06-16 GB GB0600807A patent/GB2421512B/en not_active Expired - Fee Related
- 2004-06-16 BR BRPI0411601-1A patent/BRPI0411601A/en not_active IP Right Cessation
- 2004-06-18 NL NL1026460A patent/NL1026460C2/en active IP Right Maintenance
-
2010
- 2010-01-18 AU AU2010200184A patent/AU2010200184A1/en not_active Abandoned
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699459A (en) * | 2015-12-21 | 2018-10-23 | 耐思特公司 | Aviation fuel composition |
| CN108699459B (en) * | 2015-12-21 | 2021-07-13 | 耐思特公司 | Aviation fuel composition |
| CN110249036A (en) * | 2017-01-27 | 2019-09-17 | 奈斯特化学公司 | The fuel composition of cold property with enhancing and the method for preparing it |
| US10954459B2 (en) | 2017-01-27 | 2021-03-23 | Neste Oyj | Fuel compositions with enhanced cold properties and methods of making the same |
| US11306265B2 (en) | 2017-01-27 | 2022-04-19 | Neste Oyj | Fuel compositions with enhanced cold properties and methods of making the same |
| US11795408B2 (en) | 2017-01-27 | 2023-10-24 | Neste Oyj | Fuel compositions with enhanced cold properties and methods of making the same |
| CN110582554A (en) * | 2017-05-01 | 2019-12-17 | 埃克森美孚研究工程公司 | Jet fuel treatment for blend compatibility |
| CN110582554B (en) * | 2017-05-01 | 2023-08-25 | 埃克森美孚科技工程公司 | Jet Fuel Treatment for Blend Compatibility |
| CN110616093A (en) * | 2019-08-28 | 2019-12-27 | 刘明波 | High-cleanness diesel fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2010200184A1 (en) | 2010-02-04 |
| GB0600807D0 (en) | 2006-02-22 |
| US20070187292A1 (en) | 2007-08-16 |
| CN100465251C (en) | 2009-03-04 |
| NL1026460A1 (en) | 2004-12-21 |
| BRPI0411601A (en) | 2006-08-08 |
| GB2421512B (en) | 2008-10-29 |
| NL1026460C2 (en) | 2005-10-11 |
| WO2005001002A3 (en) | 2005-12-15 |
| ZA200600302B (en) | 2007-05-30 |
| AU2004252510A1 (en) | 2005-01-06 |
| GB2421512A (en) | 2006-06-28 |
| WO2005001002A2 (en) | 2005-01-06 |
| JP2007520579A (en) | 2007-07-26 |
| AU2004252510B2 (en) | 2010-03-11 |
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