CN101711274B - Fischer-tropsch jet fuel process - Google Patents

Fischer-tropsch jet fuel process Download PDF

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CN101711274B
CN101711274B CN200880018386.1A CN200880018386A CN101711274B CN 101711274 B CN101711274 B CN 101711274B CN 200880018386 A CN200880018386 A CN 200880018386A CN 101711274 B CN101711274 B CN 101711274B
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kerosene
logistics
aromatize
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CN101711274A (en
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A·德克拉克
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Sasol Technology Pty Ltd
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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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
    • C10G69/10—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha hydrocracking of higher boiling fractions into naphtha and reforming the naphtha obtained
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4025—Yield
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a Fischer-Tropsch jet fuel refining process which has a jet fuel yield in excess of 60% by mass, said process including at least four of the following five conversion processes: a. hydrocracking one or more of a FT kerosene and heavier material fraction and a C9 and heavier FT syncrude fraction; b. oligomerising an FT syncrude fraction including hydrocarbons in the range C2to C8; c. hydrotreating one or more of an FT syncrude fraction, a product from process b.,and an alkylated FT syncrude fraction; d. aromatizing one or more of an FT syncrude fraction including hydrocarbons in the range C2 to C8, a product from process a., a product from process b, a product from process c., and a product from an aromatic alkylation process; and e. alkylating one or more of an FT syncrude fraction including hydrocarbons in the C2 to C6 range, a product from process b., and a product from process d.

Description

Fischer-tropsch jet fuel preparation method
Technical field
The present invention relates to a kind of method that synthetic crude by preparing by Fischer-Tropsch process prepares jet fuel.
Background technology
Fischer-tropsch (FT) is synthetic to be used for by synthesis gas (synthetic gas)-main hydrogen (H 2) and the gaseous mixture of carbon monoxide (CO)-preparation synthin existing for a long time.
FT is synthetic is the chemical reaction that carries out with metal oxide catalyst, and wherein reactive metal comprises iron (Fe), cobalt (Co), ruthenium (Ru) and nickel (Ni).These catalyzer can prepare by precipitating action, or take metal oxide such as aluminum oxide, titanium dioxide, zirconium white, magnesium oxide etc. as carrier.
The synthetic principal reaction of FT can be described below:
2H 2+CO→-[CH 2]-+H 2O
In this reaction-[CH 2]-represent paraffins-sometimes also referred to as alkane-Major Tectonic Units.
The method high temperature in 200-400 ℃ of scope and being up under the high pressure of 40bar-g is usually carried out.It can carry out in multiple reactor design, and is as tubular fixed-bed in (i), and (ii) 3-starches attitude bed (having another name called bubble-plate column) mutually, (iii) high temperature circulation bed and (iv) 2-fluidized-bed mutually.Be described in detail in the works document of the Fischer-Tropsch Technology (Elsevier, 2004) that edits as AP Steynberg and ME Dry.
Described reaction is carried out with chainpropagation mechanism as known in the art.Above-mentioned reaction repeatedly can prepare the long-chain material that is up to 100 carbon atoms.Often be called as in the prior art elementary FT product by this synthetic product that obtains, it contains very wide distillation range, comprises FT hydrocarbon gas (C2 to C4), FT product liquid (C5 to C21) and solid FT product (C22 and heavier) under room temperature condition.Also this mixture is called synthetic crude at a lot of publications in as " Processing ofFischer-Tropsch Syncrude and Benefits of Integrating its Products withConventional Fuels " (NPRA Paper AM-00-51,2000).
Can be under processing conditions that FT is synthetic Primary product or synthetic crude be separated into a plurality of liquid streams, C3 to C5 scope for example, petroleum naphtha C6 to C8 scope and C9 and heavier scope.
No matter in purifying fuel factory be refine crude oil, fischer-tropsch synthetic crude, liquefied coal coil (coalliquids), resinous shale or Tar sands, the product scope of usually producing all may comprise kerosene(oil)fraction.
Preparing the most common refining approach of jet fuel (Jet A-1) by the material of kerosene scope is hydrogen treatment.Wish in some cases the material of the more kerosene scopes of preparation with final raising jet fuel output, for example United States Patent (USP) 4,409, and 092 has advised doing so.
Recently, U.S. Department of Defense shows great interest to military universal fuel, especially by synthetic method preparation, to improve energy security (Forest etc., 2005).So-called future war is closely similar with jet fuel on specification with fuel (BUFF), but it has stricter flash-point specification (60 ℃ as JP-5).Ideally, such synthol refinery should only produce kerosene scope material.Although can design in principle " only jet fuel " refinery, the output of obtainable kerosene scope material is limited in practice.Even method for transformation well known in the prior art is high to the kerosene selectivity, as transform propylene (Jones 1954) with solid phosphoric acid, can not only generate kerosene scope material.
Straight run fischer-tropsch product has some inherent defects aspect Jet A-1 and/or BUFF specification reaching, and namely high linearity causes high zero pour and low temperature viscosity and lower aromatic content.In addition, the Anderson-Schultz-Flory that is usually used in describing the carbon number distribution of fischer-tropsch product distributes and shows, no matter Fischer-Tropsch process is how, and the finite volume of straight run synthetic crude in the kerosene scope.Use Anderson-Schultz-Flory to describe and show that the virgin kerosene product by the Fischer-Tropsch process preparation can make its chainpropagation probability factor (α-value) preferably realize optimizing by adjusting Fischer-Tropsch catalyst in the 0.76-0.86 scope.Most of present business fischer-tropsch technology operate outside this scope, and high temperature fischer-tropsch (HTFT) technology is with less than α-Value Operations of 0.7, and low temperature fischer-tropsch (LTFT) technology is usually with greater than α-Value Operations of 0.9.Yet even the fischer-tropsch method for transformation that is optimized for preparing kerosene scope material, the straight run productive rate of kerosene is also lower than 30%.But, be known by the synthetic jet fuel component of fischer-tropsch product and composition thereof in the prior art to prepare semi-synthetic jet fuel and complete synthesis jet fuel.
In this context, it is C9 to C16 that kerosene can be regarded as carbon number range, and boiling spread is the cut from 149 ℃ to 288 ℃ usually, but can there be variation in this definition.
Prepare Jet A-1 by low temperature fischer-tropsch (LTFT) hydrocracking product by distillation and generate a small amount of C 8-C 13Cut, it satisfies most of specification, but aromatic content is lower than Jet A-1 desired 8%.
The initial boiling point of material is subjected to the flash-point specification limits of jet fuel, and full boiling point is subjected to Jet A-1 specification limits (being 300 ℃ to the maximum).Yet in practice, normal the requirement hanged down full boiling point to reach zero pour specification (being-47 ℃ to the maximum).Also pointed out low temperature viscosity by the kerosene scope material of low temperature fischer-tropsch (LTFT) synthetic crude preparation can have problems too greatly due to viscosity (Lamprecht 2006).
The LTFT hydrocracker of Shell design---all industrialization is used in the solution-air transfer equipment of Shandong (Bintulu) the Malaysian people as them---can be carried out maximum kerosene pattern operation, it is reported that it can be refined into 50% LTFT synthetic crude kerosene scope material, and the petroleum naphtha of operation acquisition is only mixing element with distillating product thus, is not the transport fuel that reaches motor gasoline and diesel fuel specifications.
By high temperature fischer-tropsch (HTFT) hydrogenation virgin kerosene with prepare Jet A-1 by the oligomeric isoalkane kerosene that obtains of short chain olefin that uses solid phosphoric acid (SPA) to carry out and satisfy all specifications that comprise density, but regrettably producible finite volume.
Need a kind of synthol device that can make the kerosene maximum production, and described kerosene reaches Jet A-1/JP-8 and/or JP-5/BUFF specification.
Having determined needs so prevailing refinery of kerosene, and the petroleum naphtha that jointly prepares in this factory and overhead product are easy to refining and reach final fuel specification, rather than must sell with petroleum naphtha or overhead product mixture material.In the situation that refinery is positioned at away from this intermediate product market, or in the situation that refinery as the strategic asset of the military fuel of preparation, this is particularly suitable.
Summary of the invention
First aspect of the present invention provides a kind of jet fuel productive rate to surpass the fischer-tropsch jet fuel method of refining of 60 quality %, and described method comprises at least four in following five conversion processes:
One or more following materials of-a. hydrocracking: FT kerosene and heavier material cut, and C9 and heavier FT syncrude fraction;
The oligomeric FT syncrude fraction that comprises the hydro carbons in C2 to C8 scope of-b.;
One or more following materials of-c. hydrogen treatment: the product of FT syncrude fraction, process b. and alkylating FT syncrude fraction;
One or more following materials of-d. aromatize: comprise the FT syncrude fraction of the hydro carbons in C2 to C8 scope, the product of process a., the product of process b., the product of process c. and the product of alkylation of aromatic compounds process; With
One or more following materials of-e. alkylation: comprise the FT synthetic crude lightweight condensate fraction of the hydro carbons in C2 to C6 scope, the product of process b. and the product of process d..
Productive rate can surpass 70%.
Oligomerization process b. comprises the FT syncrude fraction of oligomeric C3 to C8.
Oligomerization process b. comprises the FT syncrude fraction of oligomeric C6 to C8.
Aromatize process d. comprises the FT syncrude fraction of oligomeric C3 to C8.
Alkylation process e. comprises the FT syncrude fraction of alkylation C2, optimal ethylene FT syncrude fraction.
Alkylation process e. comprises the FT syncrude fraction of alkylation C3 to C6.
When conversion process b. uses the SPA catalyzer to carry out conversion process b. and e. can in conjunction with.
In one embodiment, process d. and e. can in conjunction with.
Can select oligomerization process b. with the oligomeric one-tenth kerosene of FT condensation product range hydrocarbons class, keep simultaneously and/or give cold flow properties.
Described FT condensation product can comprise FT hydrocarbon gas and FT petroleum naphtha.
Described FT condensation product can comprise the hydro carbons in C3 to C8 scope.
Selective hydrogenation treating processes c. also removes oxidation products with preparation kerosene to remove alkene.
Hydrogen treatment process c. comprises the FT synthetic crude naphtha fraction of hydrogen treatment C6 to C8.
Can select aromatize process d. to prepare aromatic compound rather than to exist with octane itself.
The aromatize process can transform the petroleum naphtha of hydrocracking process a..
Can select aromatize process d. with preparation H 2, benzene, toluene, ethylbenzene, dimethylbenzene, and the aromatic compound of kerosene scope.
Can select aromatize process d. to avoid generating simultaneously double-core aromatic compound such as naphthalene, its smoke point to kerosene scope material has disadvantageous effect.
Can select alkylation process e. to prepare aromatic compound in the kerosene boiling spread with the multiple alkylation that increases aromatic compound with ethene, reduce simultaneously the ethene in product.
Can select alkylation process e. to reduce the multiple alkylation of aromatic compound so that the maximum production of the alkyl-aromatic compounds in the kerosene boiling spread with alkene.
Hydrocracking can be in the hydrocracking zone of containing hydrocracking catalyst, carry out under the hydrocracking condition/implement.
Oligomeric can be in the oligomeric zone of containing oligomerisation catalyst, carry out under oligomeric condition/implement.
Hydrogen treatment can be in the hydrogen treatment zone of containing hydrotreating catalyst, carry out under the hydrogen treatment condition/implement.
Aromatize can be in the aromatize zone of containing the aromatize catalyzer, carry out under the aromatize condition/implement.
Alkylation can contain the alkylation zone of alkylation catalyst, carry out under alkylation conditions/implement.
Usually can be considered for refining techniques of the present invention comprises:
Figure G2008800183861D00051
Figure G2008800183861D00061
Think that above-mentioned technology makes refinery can satisfy in the high yield preparation the fully synthetic jet fuel of international jet A-1 specification, and the common chemical that produces and/or other transport fuels be when also can satisfy fuel specification such as Europe-4, reduced complexity.
Such refinery can overcome by straight run and distillates some restrictions that productive rate, high linear (high-solidification point) and low aromatic content are brought.
According to the type of skill of selecting and the order of conversion unit, can improve the amount that satisfies the jet fuel specification and the quality of other products.This is actually another favourable part of the present invention, because it is more flexible, so its permission adjusts secondary product, and can satisfy the needs of different refining techniquess.
Embodiment
Now by only as nonrestrictive example and with reference to flow chart description the present invention of enclosing.
But the present invention's example is illustrated as the method for Fig. 1, and described method is optimized to prepare maximum kerosene scope material by the fischer-tropsch synthetic crude.Described FT synthetic crude can have following composition usually:
Hydro carbons scope % by weight
C2 material 13.0%
C3-C5 material 43.1%
C6-C8 cerebrol 24.5%
The above material 19.5% of C9
The only combination of following conversion process of the method utilization of Fig. 1: hydrocracking (unit [a]), oligomeric (unit [b]), hydrogen treatment (unit [c]), aromatize ([d]) and alkylation (unit [e]).
Kerosene scope material satisfies international Jet A1 specification, reaches stricter BUFF flash-point specification if adjust separating step, also optionally as BUFF.
First conversion unit of the method for Fig. 1 is unit [a], wherein hydrocracking part under the hydrogenation isomerization conditions, part carries out under the hydrocracking condition.It is known in the prior art that hydrocracking is used for preparing kerosene by synthetic crude.As is known in the art, the catalyzer that is used for this conversion is bifunctional, comprises acid and metal site.With regard to feed composition and unit structure, its application within the scope of the present invention be different from well known in the prior art those.
Olefin oligomerization is second conversion unit---unit [b] becomes known for preparing kerosene scope material by the light olefin material in the prior art.The selection of oligomerisation catalyst has material impact to products distribution and character.In the present invention, preferred embodiment is based on the olefin oligomerization process of solid phosphoric acid (SPA) catalysis or soft silica-aluminum oxide (ASA) catalysis, but the present invention is not subjected to the restriction of these types.Charging can be by hydrocarbon gas, C normally 2-C 5Logistics 3a, and petroleum naphtha, normally C5 and more heavy substance logistics 3b consist of.Feed pretreatment is optional, but will consider the inherent limitations of the catalyzer selected.For example, the mixture of hydro carbons and the common oxidation products of fischer-tropsch synthetic crude can be offered ASA, but SPA resistance to oxidation product ability is relatively poor.This step of converting has three kinds of primary products, i.e. light hydrocarbon, normally C 2-C 8Logistics 4a; Petroleum naphtha, normally C 9-C 14Logistics 4b; And overhead product, normally C 15Reach the more logistics 4c of weight.The ratio of these products and composition will depend on the type of oligomerization process.For example, select the SPA catalyzer will not generate C 15Reach the more distillate flow 4c of weight.The quality of the product that needs and productive rate also can be optimized by the skilful use internal recycle.This conversion process comprises as other aspects of instructing in prior art, for example loops heat management by alkane.
Transform because oligomerization process is unsuitable for alkane, therefore can olefinic naphtha and lighter products in logistics 4a be exhausted by circulation, the alkane in this logistics consume.Alkane in logistics 4a can consider as final product, for example C3-C4 can be used as LPG or combustion gas and C5+ as petroleum naphtha, or as the charging of aromatize unit [d].Alkene in logistics 4a is circulated to that to exhaust be not precondition yet.The mixture that contains alkene also can be used as final product, and for example, C3-C4 can be used as LPG or combustion gas, and C5+ is as petroleum naphtha, as the charging of aromatize unit [d], as alkylation [e] or be hydrogenated the charging of the unit [c] of processing.
From the kerosene products logistics 4b of oligomeric generation can be hydrogen treatment unit [c] hydrogenation to improve stability in storage.
From oligomeric generation distillate product logistics 4c can be unit [a] by with the common charging of internal recycle of hydrocracking unit and hydrocracking.By with the common charging of the internal recycle of hydrocracker, but the limit excessive cracking improves the kerosene productive rate.A preferred embodiment of the present invention is that at first distillate flow 4c is sent to hydrotreater unit [c], then is used as the feed stream 5c of hydrocracker unit [a].So operation further reduces excessive fragmentation and improves the kerosene productive rate.
The 3rd conversion unit is hydrotreater unit [c], and it is used for improving the stability in storage of kerosene, and reaches specification such as the acid number relevant to oxidation products.It also is used for providing some feed pretreatment for some processes such as aromatize unit [d], if the described pretreated words of the aromatize Technology Need of selecting.The catalyzer that uses is metal-modified hydrotreating catalyst well known in the prior art.Its in the present invention purposes and described in the prior as broad as long, but feed stream 3b, 4a, 4b and 4c consist of the incoming mixture of distinctive olefin oligomer and straight run fischer-tropsch synthetic crude.The product of this conversion process usually and charging be isomorphism, but oxidation products and alkene are converted into alkane.The differentiation of three primary products is based on distillation range, i.e. gas and petroleum naphtha, C normally 3-C 8Logistics 5a, kerosene, C normally 9-C 14Logistics 5b, and overhead product, C normally 15Reach the more logistics 5c of weight.This conversion process comprises as other aspects of instructing in prior art, charging as common in hydrogen.
Gas and naphtha products logistics 5a can be used as final product, and as motor gasoline, or it can be used as the charging of aromatize unit [d].Preferred purposes depends on type and the product composition of oligomeric technology of type, the use of the aromatize technology of selecting, i.e. oligopolymer and/or straight run fischer-tropsch synthetic crude.Its product is the mixture of the oligopolymer of hydrotreated FT synthetic crude and [b] generation.Yet described composition depends on idiographic flow used.
It is isoalkane kerosene (IPK) that kerosene products logistics 5b is also referred to as, and it is considered to the splendid composition of jet fuel in the prior art.
As previously mentioned, distillate product logistics 5c and can be used as the charging of hydrocracker unit [a] to improve the kerosene productive rate.
The 4th conversion unit is aromatize unit [d].The preparation of this process need to reach the aromatic compound of jet fuel specification, also provides hydrogen for the process of the consumption hydrogen that describes in detail in the present invention simultaneously.The selection of the feed composition of this element--- logistics 2a, 4a and/or 5a---depending on aromatize technology is divided into two major technique types.
First kind aromatize process is the petroleum naphtha aromatize, the charging (C that it need to be in naphtha range 6Heavier).A preferred embodiment of the present invention is used the aromatize process based on nonacid Pt/L zeolite, and it is suitable for a class petroleum naphtha aromatize type of fischer-tropsch Substance Transformation for the utmost point.But also Application standard catalystic reforming method, its chlorinated aluminas based on the platinum modification (chlorided alumina) catalyzer, but efficient is lower in this application.This can understand from the feed properties aspect, and nonacid Pt/L-zeolite process is conducive to straight chain hydrocarbon (the fischer-tropsch synthetic crude is rich in straight chain hydrocarbon), and the Pt-alumina process is conducive to be rich in the charging of naphthenic hydrocarbon.In both cases, charging all needs pre-treatment to remove heteroatoms, and described pre-treatment is carried out in hydrocracking unit [a] and hydrogen treatment unit [c].
Equations of The Second Kind aromatize process is the light hydrocarbon aromatize, and it can transform by C 3The charging that heavier hydro carbons consists of.This type of aromatize process is wherein the most often used metal Ga and Zn based on metal-modified H-ZSM-5 zeolite catalyst.This conversion is the H-ZSM-5 catalyzer realization of available non-modification also, but is not preferred embodiment, needs metal because desorption is molecular hydrogen.More can tolerate heteroatomic compound such as oxidation products in charging based on the process of ZSM-5, and charging can be used without hydrotreated logistics 4a in advance.Yet known in the state of the art, oxidation products is disadvantageous to catalyst life and charging selection, can consider untreated logistics 4a charging and pretreated logistics 2a charging and/or logistics 5a charging or the combination of one of them.
The type of aromatize process has not only determined the charging requirement, has also determined product structure, and product structure can be different with different methods.In petroleum naphtha aromatize process, any C that forms in this process 5Lighter hydro carbons can be considered to the fatal conversion to described product, because it can not change into aromatic compound by circulation.On the contrary, in light hydrocarbon aromatize process, C 3Heavier hydro carbons can be recycled to improve the aromatic compound productive rate.Although these differences are arranged, prepare three kinds of primary product cuts in the aromatize process, i.e. light gas, normally hydrogen and C 1-C 2 Hydrocarbon material flow 6a; Gas and light naphtha, C normally 3-C 6 Hydrocarbon material flow 6b; With the petroleum naphtha that is rich in aromatic compound, be generally C6 and heavier aromatic compound and C 7And heavier hydrocarbon material flow 6c.Comprise other chargings well known in the prior art and product logistics.
Light gas logistics 6a is the product that is rich in hydrogen.It is splendid hydrogen source, and hydrogen can be by method recovery well known in the prior art, as pressure-variable adsorption.According to method and product structure, it can be hydrocracking unit [a] and hydrogen treatment unit [c] conversion process provides sufficient hydrogen.Excessive hydrogen may be output to the fischer-tropsch gas circulation to improve the synthetic crude productive rate.According to the fischer-tropsch technological property, the hydrogen-depleted gas body can be used as combustion gas, or as the charging for preparing synthesis gas.
Gas and light naphtha logistics 6b form and depend on the aromatize process.In the situation that the petroleum naphtha aromatize, it is alkane substantially, can be used as liquefied petroleum gas as final product, is used for mixing and/or combustion gas.This product circulates hardly, although be possible in theory.If select light naphtha aromatize process, it can be circulated to and exhaust, or according to its olefin(e) centent, it also can be sent to oligomeric unit [b] or alkylation [e].
The naphtha stream 6c that is rich in aromatic compound is the source that need to reach the aromatic compound of jet fuel aromatic compound specification.This product of part can directly be used as final fuel, is sent to alkylation process unit [e] but a preferred embodiment of the present invention is at least part of this product.
The aromatic compound for preparing in the aromatize process in unit [d] is mainly at C 6-C 9In the aromatic compound scope.Not all aromatic compound all can directly mix in kerosene, because this will cause the jet fuel flash-point too low.This shortcoming can be by overcoming with the molecular-weight average that improves aromatic compound with the olefin alkylation aromatic compound in alkylation process unit [e].Select charging composition alkene and aromatic compound to consist of, and the type of alkylation process and operation are so that the maximum production of kerosene scope aromatic compound.
Can carry out prefractionation to increase the C in charging to aromatic compound feed stream 6c 6-C 8The aromatic compound cut, but this is not prerequisite.If suitable, the alkene charging can directly come from fischer-tropsch hydrocarbon gas logistics 3a, from oligomeric logistics 4a contain the alkene light hydrocarbons and from olefin-containing gas and the naphtha products of aromatize logistics 6b.Can be arbitrarily suitable array configuration is selected these chargings.
In a preferred embodiment of the invention, olefin oligomerization unit [b] and alkylation of aromatic compounds unit [e] process can be combined into a process.This conversion unit number that the present invention will be needed is reduced to four from five.Yet, those that this preferred embodiment is instructed the catalyzer selectional restriction in the prior art.If alkylation and oligomericly carry out independently of each other, the catalyzer of this process is selected to expand to comprise for example catalyst type of zeolite.In another feasible embodiment of the present invention, alkylation can independently be carried out, but this moment alkylation also to carry out part oligomeric to alleviate the burden of oligomeric unit.
Can carry out in such a way alkylation process, namely it mainly generates kerosene products logistics 7b, but also can form some more low-boiling point material logistics 7a.As instructing in prior art, this may need recycle of portion of product or comprise the transalkylation step so that the kerosene maximum production.According to oligomeric level in this unit, kerosene as may be in hydrotreater unit [c] before jet fuel the alkene in the hydrogen treatment kerosene(oil)fraction.Comprise other chargings well known in the prior art and product logistics.The described kerosene products of part also can be mixed with other fuel Products or is used as final product, as isopropyl benzene.
Embodiment
The following example example explanation the present invention, but should not be considered to limit by any way the present invention.
Embodiment 1
Jet fuel refinery design in the present embodiment as shown in Figure 2 is based on the charging available from HTFT.The target of the present embodiment is to show can prepare how many jet fuels from the fischer-tropsch synthetic crude with the present invention.
Fischer-tropsch C 9And heavier synthetic crude (boiling point usually＞130 ℃) as the feed stream 1 of hydrocracker unit [a], described hydrocracker unit [a] operates according to description of the invention.C available from olefin oligomerization logistics 4c 16And heavier overhead product scope product (boiling point usually＞280 ℃) at first is hydrogenated to process and produces logistics 5c, then also is hydrogenated cracking.Result is prepared the logistics 2b that is mainly kerosene, and in fresh feed, productive rate is 75% left and right.C 3-C 8 Light hydrocarbons logistics 2a is sent to aromatize unit [d].
Fischer-tropsch C 6-C 8Synthetic crude (boiling spread is generally 40-130 ℃) is used as the feed stream 3b of oligomeric unit [b] without pre-treatment.Oligomerization process is used the ASA catalyzer, and it can process the oxidation products that exists in described charging.The C for preparing in oligomerization process 8And lighter hydrocarbon material flow 4a is sent to the aromatize unit.C 9And heavier hydrocarbon product logistics 4b and 4c is hydrogenated processing, the saturated products of generation isomorphism in unit [c].Hydrotreater unit [c] also hydrogen treatment available from the kerosene range mixture of the oligomeric of alkylation [e] and alkylate logistics 7b, so that olefin saturated and improve the stability in storage of final product.Kerosene scope product logistics 5b is a kind of jet fuel component, and overhead product logistics 5c is sent to hydrocracker unit [a] as mentioned above.
Aromatize unit [d] is based on the method for using metal-modified H-ZSM-5 catalyzer.The feed stream of this element comprises the C available from hydrocracker logistics 2a 3-C 8Hydro carbons, available from the C of oligomeric logistics 4a 5-C 8Hydro carbons and available from the C of alkylation logistics 7a 3-C 4Hydro carbons.The aromatize unit operates to transform C with internal recycling 3-C 6Hydro carbons (lower than benzene boiling point).Light gas logistics 6a is as the required sources of hydrogen of refining.Naphtha fraction (boiling spread is between benzene and dimethylbenzene) is sent to alkylation logistics 6b, and the heavier aromatic compound cut in the kerosene boiling spread is as jet fuel component logistics 6c.
The C that comprises in the product of aromatize logistics 6b 6-C 8Aromatic compound is rich in the fischer-tropsch C of alkene 3-C 5Feed stream 3a alkylation.Use is based on the alkylation oligomerization process of the combination of SPA catalyzer, and it also becomes kerosene with excessive olefin oligomerization not only with alkylation of aromatic compounds.C 5-C 8Product logistics 7a iiThereby retained the final petroleum naphtha forming section of conduct so-called " fatal petroleum naphtha output ", thereby avoided the accumulation of inert substance in refinery's recycle stream, and C 3-C 4Cut logistics 7a iLoop back aromatize unit [d].Before being used as the jet fuel component, 7b carries out hydrogen treatment so that olefin saturated to the logistics of kerosene scope product.
The petroleum naphtha that this refinery's design produces: the ratio of kerosene is 11: 89, and kerosene(oil)fraction reaches the specification of fully synthetic Jet A1.The aromatic content of petroleum naphtha is low, but is rich in alkene, needs further refining to be used as transport fuel.Being summarized in table 1 of the logistics of considering provides, and report is based on total fischer-tropsch synthetic crude 500000kg/h meter (not comprising water-gas shift gas).Refinery's design of the present embodiment does not have display process fischer-tropsch C 1-C 2Hydro carbons or be dissolved in the oxidation products of the synthetic aqueous product of fischer-tropsch.Chemical such as ethene, ethanol, acetone, Virahol, n-propyl alcohol and methyl ethyl ketone can reclaim from these cuts by currently known methods of the prior art.C 3And heavier oxidation products also can be converted to alkene, and with other FT C 3-C 5Feed stream 3a processes together, to increase the volumetric production of jet fuel on identical fischer-tropsch charging basis.
The logistics general introduction shown in Figure 2 of table 1. embodiment 1
Figure G2008800183861D00131
Embodiment 2
The design of jet fuel refinery in the present embodiment is based on the charging identical with embodiment 1 as shown in Figure 3.Difference is the selection of oligomeric, aromatize and alkylation process.The target of the present embodiment is to show that the present invention also can make the jet fuel maximum production, and petroleum naphtha reaches motor gasoline specification (Europe-4) simultaneously.Another target of the present embodiment is to illustrate that how to integrate the aftertreatment of fischer-tropsch aqueous product favourable.
Hydrocracker unit [a], it operates according to the present invention, with fischer-tropsch C 9And heavier synthetic crude logistics 1 changes into kerosene stream 2b and lighter product logistics 2a.C only 6-C 8Cut logistics 2a iiBe sent to aromatize unit [d], and C 3-C 5Cut logistics 2a iBe sent to oligomeric unit [b] to be used as the required thinner of heat management.
Thereby be combined into a unit [b/e] by using the SPA catalyzer that operates that oligomeric and alkylation are transformed in being rich in the conversion of olefines mode.This can save independently alkylation.The feed stream of this unit is fischer-tropsch C 3-C 5Cut logistics 3a, available from hydrocracker logistics 2a iC 3-C 5Cut, available from aromatize unit logistics 6b iBenzene and available from the olefin stream of fischer-tropsch aqueous product refinery steams 8.Available from the alkene of aqueous product refining usually by the carbonyl compound selective hydration is become pure and mild with C 3Reaching heavier dehydration of alcohols is that alkene prepares, as described in the prior art.In the olefin oligomerization and alkylation of aromatic compounds process of this combination, benzene mainly is converted into isopropyl benzene, forms less heavier aromatic compound.This does not disturb normal oligomerization process.The product of this process is C 3-C 4Liquefied petroleum gas logistics 4a i, unhydrided C 4-C 8 Motor gasoline logistics 4a ii, and the naphtha stream 4a that is sent to hydrotreater unit [c] iiiWith kerosene stream 4b cut.The characteristics of using the conversion of SPA catalyzer are very lower than the output of kerosene material heavily, and in prior art, usual way is to remove logistics with a little bottom to remove these products.
Hydrotreater unit [c] hydrogen treatment fischer-tropsch C 6-C 8The alkene that exists in naphtha stream 3b and oxidation products, and available from combination oligomeric-the logistics 4a of alkylation iiiProduct with 4b.Although hydrogenation can be carried out in independent unit, charging and product point should separate so that the fischer-tropsch petroleum naphtha can not mix with oligomerization product.This makes this unit can use more excellent catalyzer load mode, and improves the oeverall quality of final product.Hydrogen treatment also can independently carried out in reactor.Hydrogenated kerosene logistics 5b is a kind of jet fuel component, and hydrotreated naphtha range oligomerization product logistics 5a iIt is a kind of motor gasoline component.Hydrotreated fischer-tropsch C 6-C 8Naphtha stream 5a iiCharging as aromatize unit [d].
Aromatize unit [d] is based on nonacid Pt/L-zeolite catalysis process.Charging is available from hydrocracking logistics 2a iiWith hydrogen treatment logistics 5a iiC 6-C 8Petroleum naphtha in scope.This process has higher hydrogen and aromatic compound productive rate.Hydrogen can reclaim from lightweight gas stream 6a, and surpasses the demand of hydrocracking and hydrogen treatment unit [a] and [c].Described hydrogen may be output to the fischer-tropsch gas circulation, and this has Beneficial Effect to the synthetic crude productive rate.The present embodiment has shown this potential benefit, but no longer carries out the example explanation.Separate naphtha products and obtain benzene logistics 6b i, liquid petroleum gas distillations stream 6b iiWith aromatic gasoline stream 6b iiiThe kerosene output of this class aromatize process depends on charging, does not form the material of kerosene as charging under this particular case.
In the present embodiment, the product of refinery's output is comprising that available from fischer-tropsch aqueous product and refining motor gasoline: the proportion of products of jet fuel is 28: 72 to the ethanol that reaches 10% oxidized product specification.The motor gasoline that calculates and jet fuel character provide in table 2.
The motor gasoline that calculates of the embodiment 2 that table 2. is shown in Figure 3 and jet fuel character
Figure G2008800183861D00151
Being summarized in table 3 of the logistics of considering provides, and report is based on total fischer-tropsch synthetic crude 500000kg/h meter (not comprising water-gas shift gas).Process fischer-tropsch C 1-C 2Hydro carbons does not show in the present embodiment, can reclaim chemical such as ethene from it, and residuum is sold as synthetic natural gas, or used as combustion gas.The implicit refining of the present embodiment is dissolved in the oxidation products in the synthetic aqueous product of fischer-tropsch, and ethanol is purified as the motor gasoline additive, and heavier alcohols and all carbonyl compound are converted into alkene.
The general introduction of the logistics shown in Figure 3 of table 3. embodiment 2
Figure G2008800183861D00161
Embodiment 3
Improved jet fuel refinery design in embodiment 2 by the mode that changes alkylation of aromatic compounds.In the present embodiment as shown in Figure 4, use the independently alkylation based on zeolite catalyst, its operating method is the productive rate that the aromatic compound of circulation monoalkylation improves the aromatic compound of dialkyl group.In addition, select ethene to make alkylation alkene, improving the overall yield of motor gasoline and jet fuel on similar to embodiment 2 charging basis, and significantly do not change the ratio of motor gasoline and jet fuel.
Charging, operation and identical available from the product of hydrocracker unit [a] and embodiment 2.
As embodiment 2, oligomeric unit [b] is based on the process of using the SPA catalyzer.Similar in charging and embodiment 2, only difference is there is no the aromatic compound charging in this unit.Therefore product is not rich in alkyl-aromatic compounds, but mainly is made of aliphatic hydrocarbon.Product separation becomes different fractions, i.e. C 3-C 4Liquefied petroleum gas logistics 4a i, unhydrided C 4-C 8 Motor gasoline logistics 4a ii, and the naphtha stream 4a that is sent to hydrotreater unit [c] iiiWith kerosene stream 4b cut.
Similar in hydrotreater unit [c] and embodiment 2, but the composition of some logistics is different.This is particularly evident in not being rich in the kerosene feed stream 4b of alkyl-aromatic compounds.
Aromatize process unit [d] is being identical aspect charging, operation and product.Only difference is benzene cut logistics 6b iThe flow direction, it is sent to alkylation [e] now.
Alkylation [e] is based on the ethylene alkylation of the benzene that uses zeolite catalyst such as H-ZSM-22 in the present embodiment.With the key distinction of commercial preparation ethylbenzene be except using benzene logistics 6b iOuter also the use available from the ethylene/ethane mixture of fischer-tropsch made feed stream 9, and the benzene of monoalkylation is circulated to improve the productive rate of diethylbenzene together with benzene.Primary product is kerosene scope aromatic compound logistics 7b, aromatic naphthas logistics 7a iiBe rich in C 2 Combustion gas logistics 7a i
Being summarized in table 4 of the logistics of considering provides, and report is based on total fischer-tropsch synthetic crude 500000kg/h meter (not comprising water-gas shift gas).Similar in this description and embodiment 2, but comprise in the present embodiment and process fischer-tropsch C 2Hydro carbons.Motor gasoline: the proportion of products of jet fuel is 28: 72 and similar, has obtained slightly improved fuel performance although compare with embodiment 2.
The general introduction of the logistics shown in Figure 4 of table 4. embodiment 3
Figure G2008800183861D00181
Embodiment 4
Jet fuel refinery design (Fig. 5) in the present embodiment is based on the charging available from the LTFT process, and itself and Sa Suoer (Sasol) have similar synthetic crude character what the industrialized unit of the Salzburg (Sasolburg) in South Africa was produced.Same principle also is applicable to Oryx GTL device and the Malay Shell Bintulu GTL equipment of Qatar.Although the target of the present embodiment is to show between HTFT and LTFT synthetic crude on fischer-tropsch carbon number distribution and composition, very large difference to be arranged, but the present invention is applicable to both, and be not subjected to the α of Fischer-Tropsch catalyst-value restriction (therefore, yet can consider to do charging with the mixture of the synthetic crude with different carbon number distribution).
According to description of the invention operation hydrocracker (Fig. 5, unit [a]).The main charging of this unit is available from the synthetic C of low temperature fischer-tropsch 9And heavier cut (Fig. 5, charging 1).Different from the HTFT charging, the LTFT charging of this unit comprises (＞50%) " resistates " or wax distillate in a large number.Hydrotreated C available from olefin oligomerization 16And heavier cut (Fig. 5, logistics 5c) also is fed to hydrocracker.Two of this unit primary product is the C as aromatize (Fig. 5, unit [d]) charging 3-C 8The kerosene (Fig. 5, logistics 2b) of light hydrocarbons (Fig. 5, logistics 2a) and the final jet fuel component of conduct.
Can isolate C from the LTFT product gas under pressure 3And heavier hydro carbons, need not subcooling.C 4-C 8Cut (Fig. 5, logistics 3b) is as the charging (Fig. 5, unit [b]) of oligomeric unit.Oligomerization process is used the ASA catalyzer that can process the oxidation products that exists in charging.By some light olefins and most of C 4Lighter products (Fig. 5, logistics 4a that alkane consists of i) can be used as liquefied petroleum gas (LPG) (LPG), motor gasoline blending ingredients or be sent to aromatize unit (Fig. 5, unit [d]).It is as LPG in the present embodiment.Naphtha products is C 5-C 8The mixture of alkene and alkane (Fig. 5, logistics 4a ii), it can be hydrogenated processing or be used directly as olefinic naphtha as in the present embodiment.It also can be used as the charging of aromatize unit.Kerosene (Fig. 5, logistics 4b) and heavier overhead product (Fig. 5, logistics 4c) are hydrogenated processing in olefin hydrogenation is processed (Fig. 5, unit [c]).The kerosene of hydrogenation (Fig. 5, logistics 5b) is a kind of final jet fuel component, and the overhead product of hydrogenation (Fig. 5, logistics 5c) is used as the charging of hydrocracker (Fig. 5, unit [a]).
Aromatize unit (Fig. 5, unit [d]) is based on the process of metal-modified H-ZSM-5 catalysis.The charging of this unit is by the C available from hydrocracker 3-C 8Hydro carbons (Fig. 5, logistics 2a) consists of.Noticed that aromatic compound output can further improve by also using petroleum naphtha (Fig. 5, logistics 4a) available from oligomerization process to do charging, but not so operation in the present embodiment.The operation of aromatize unit uses internal recycle to transform C 3-C 6Hydro carbons (lower than benzene boiling point), but also can consider single-pass operation.Can be from the light gas (Fig. 2, logistics 6a) recover hydrogen, and the residuum of light gas can be used as combustion gas.Heavier product is fractionated and distinguishes application.The cut (Fig. 5, the logistics 6b that contain all benzene and some toluene i) as the aromatic compound charging of alkylation (Fig. 5, unit [e]).Contain residual toluene and number of C 8The cut of aromatic compound is retained as petroleum naphtha (Fig. 5, logistics 6b ii), and heavier kerosene(oil)fraction is used as jet fuel composition (Fig. 5, logistics 6b iii).
With the LTFT C that is rich in propylene 3Cut carries out alkylation of aromatic compounds (Fig. 5, unit [a]).This unit operates in the alkylation mode, and as is known in the art, the internal recycle aromatic compound is to limit oligomeric side reaction.The technology of using can be based on solid phosphoric acid (SPA) or zeolite catalyst.Use in the present embodiment the technology based on SPA to limit multiple alkylation.The product of this unit is for usually being rich in light gas (Fig. 5, the logistics 7a of propane i), petroleum naphtha (Fig. 5, logistics 7a ii), and the aromatic compound kerosene (Fig. 5, logistics 7b) of the final jet fuel component of conduct, it optionally carries out hydrogenation retouching (hydropolish) to improve stability in storage.
Being summarized in table 5 of the logistics of considering provides, and report is based on total fischer-tropsch synthetic crude 500000kg/h meter (not comprising water-gas shift gas).Display process fischer-tropsch C1-C2 hydro carbons and be dissolved in the oxidation products of aqueous product not in the present embodiment.Motor gasoline: the proportion of products of jet fuel is 21: 79.Described jet fuel meets Jet A1 specification, can not think final transport fuel but described motor gasoline aromatic content is too high.
The general introduction of the logistics shown in Figure 5 of table 5. embodiment 4

Claims (10)

1. a jet fuel productive rate surpasses the fischer-tropsch jet fuel method of refining of 60 quality %, and described method comprises at least four in following five conversion processes:
One or more following materials of-a. hydrocracking: FT kerosene reaches more heavy substance cut and C9 and heavier FT syncrude fraction;
The oligomeric FT syncrude fraction that comprises hydro carbons in C2 to C8 scope of-b.;
One or more following materials of-c. hydrogen treatment: the product of FT syncrude fraction, process b. and alkylating FT syncrude fraction;
One or more following materials of-d. aromatize: comprise the FT syncrude fraction of the hydro carbons in C2 to C8 scope, the product of process a., the product of process b., the product of process c. and the product of alkylation of aromatic compounds process; With
One or more following materials of-e. alkylation: comprise the FT syncrude fraction of the hydro carbons in C2 to C6 scope, the product of process b. and the product of process d.,
Wherein said at least four conversion processes comprise oligomerization process b..
2. the process of claim 1 wherein conversion process b. and e. combination when process b. uses solid phosphoric acid catalyst to carry out.
3. the process of claim 1 wherein process d. and e. combination.
4. the method for any one in claim 1-3, wherein select oligomerization process b. to make the oligomeric one-tenth kerosene of C3 to C8FT syncrude fraction range hydrocarbons class, and keep and/or give cold flow properties.
5. the method for any one in claim 1-3, wherein hydrogen treatment process c. removes alkene, also removes in addition oxidation products with preparation kerosene.
6. the method for any one in claim 1-3, wherein select aromatize process d. to prepare aromatic compound rather than to exist with octane itself.
7. the method for claim 6, wherein aromatize process d. transforms the petroleum naphtha available from hydrocracking process a..
8. the method for claim 6, wherein aromatize process d. produces H 2, benzene, toluene, ethylbenzene, dimethylbenzene, and kerosene scope aromatic compound.
9. the method for claim 8, wherein aromatize process d. avoids generating simultaneously the double-core aromatic compound.
10. the method for any one in claim 1-3, wherein alkylation process e. increases the multiple alkylation of aromatic compound with the aromatic compound of preparation kerosene boiling spread with ethene, reduces simultaneously the ethene in product.
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