CN101720349A - Biogasoline - Google Patents

Biogasoline Download PDF

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Publication number
CN101720349A
CN101720349A CN200880016211A CN200880016211A CN101720349A CN 101720349 A CN101720349 A CN 101720349A CN 200880016211 A CN200880016211 A CN 200880016211A CN 200880016211 A CN200880016211 A CN 200880016211A CN 101720349 A CN101720349 A CN 101720349A
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Prior art keywords
oil
component
biogasoline
bio
cracking
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CN200880016211A
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Chinese (zh)
Inventor
盖尔·雷莫·弗雷德里克森
特朗德·麦斯泰德
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Equinor ASA
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Statoil ASA
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
    • 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
    • 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
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/1037—Hydrocarbon 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/28—Propane and butane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

A process for the preparation of a biogasoline component comprising: (I) obtaining at least one bio-oil and, if necessary, liquefying the bio-oil component; (II) adding the bio-oil in liquid form to a FCC unit along with at least one mineral oil; (III) cracking the components added to the FCC unit to form at least a bio-LPG fraction and a bio-naphtha fraction; (IV) alkylating or catalytically polymerising at least part of the bio-LPG fraction; and (V) combining at least a part of the product of step (IV) with at least a part of the bio-naphtha fraction to form a bio-gasoline component.

Description

Biogasoline
Technical field
The present invention relates to a kind of method that forms biogasoline by fluid catalytic cracking (FCC) that bio oil (particularly fish oil) is combined with mineral oil.
This method all is used in the fuel by guaranteeing liquefied petroleum gas (LPG) and naphtha fraction in the cracking material, with the biological content maximization in the fuel.
Background technology
The whole world promotes day by day to the concern of climate warming, and therefore the concern to Carbon emission also promotes day by day.At least in Europe, people from all walks of life are just taking the measure of highest ranking to attempt reducing emission of carbon-dioxide.This means to depend on for example renewable energy source such as sun power and wind energy more, improve the tax rate of low efficiency product, and the utilization of investing in ocean energy resources more.Another fast-developing field is a biofuel, especially for the biofuel of vehicle.
Biofuel instruction 2003 (instruction 2003/30) has been established the market share that makes biofuel and reached 5.75% indicative target value in the end of the year 2010.This reference value is based on the energy of fuel, and each member states will set national objective.In the energy of on January 10th, 2007 issue and weather package plan and relevant renewable energy source route map, EU Committee has set at the year two thousand twenty and has made the vehicle of European Union reach 10% minimum restrictive target with biofuel.
Rely on the use of the fuel flexible vehicle of alcohols, particularly ethanol (and methyl alcohol) operation, well-known.Ethanol can be by sugarcane production, and through be usually used in mixing with gasoline form biofuel (E5, E85).Yet methyl alcohol is poisonous and be not the ideal material of mass market, so its purposes is confined to the contest car now.
The biological compound that the fuel making merchant has therefore sought other the additive that acts as a fuel, and considering to utilize bio oil to make biogasoline and biofuel.Put down in writing the mild hydrogenation cracking process of vegetable oil among the US 2006/0186020, wherein vegetable oil and mineral oil and formed diesel component by cracking.
Other manufacturers then consider by with the biomaterial fluid catalytic cracking to form gasoline component.US5 has put down in writing the method for cracking vegetables oil, animal oil or natural rubber in 233,109, at US4, has discussed in 300,009 and has used zeolite that vegetable material is converted into gasoline in cracking process.These documents all are used for cracking unit with 100% biological charging, but when being used for commercial operation, biomaterial are mixed being absolutely necessary with traditional mineral oil component.Biomass can not be used to make 100% biofuel separately.
In nineteen eighty-three, a kind of mineral oil cracked method that will be mixed with vegetable oil has been proposed among the Brazilian patent application PI 8304794 of Brazilian Petroleum Co. (Petrobras).UOP (UOP) has also proposed similar process program recently.Austria's Gas Company (OMV) has also been reported by cracking and has been mixed with the mineral oil of vegetable oil and the result that obtains.Vegetable oil comprises longer chain fatty acid (with the form of triglyceride level or free fatty acids), and these chains can be in fluidized catalytic cracker cracking and form short hydrocarbon chain, therefore the possibility that forms the biogasoline component is arranged.
Yet the subject matter that biofuels such as biological example gasoline face is that the availability that will mix the biomaterial of fuel is limited.As will in all gasoline that the whole world is used, mixing the biological components of considerable part, global natural resources be can't bear the heavy load.For cultivating necessary vegetable material, need a large amount of soils, and may therefore cause further destruction global forest.Because it is a major reason that causes climate change that forest destroyed, will run counter to desire by destroying the biomass that forest obtains to be used to make biofuel.Therefore it is vital making the biomass that are applicable to biofuel production finally become fuel oil and not be wasted.
Summary of the invention
The contriver recognizes, separately the cracking bio oil or under the situation that has mineral oil to exist the cracking bio oil can produce biolith cerebrol and biological fluid liquefied oil gas (bioLPG).The contriver further recognizes, can carry out aftertreatment to the bioLPG component that generates, and then it is combined with biological naphtha fraction to form biogasoline.Adopt this method, add biomaterial in the cracking unit and surpass 50% part that can form gasoline.
In addition, the contriver finds unexpectedly, combines with mineral oil, and marine oil can be with the mode quilt successfully cracking identical with vegetable oil in FCC apparatus.Use on the booksly though in FCC apparatus vegetable oil combined with mineral oil, it is brand-new being to use marine oil, and has formed another aspect of the present invention.
Marine oil may contain high-caliber heavy metal.In these heavy metals, what have has toxicity to the conventional catalyzer that uses in the FCC apparatus, may not propose the use marine oil in the prior art for this reason.The contriver recognizes handling to the charging of the FCC apparatus of small part heavy oil (being long residuum or vacuum residuum) and has most these metals.Therefore these FCC apparatus are being used the FCC catalyzer that can tolerate a certain amount of heavy metal inherently.The contriver further recognizes, when the marine oil that will comprise heavy metal inherently (for example be lower than 50%, more preferably be lower than 30%) when mixing with the FCC charging that yet comprises these metals, the heavy metal level in the mixture remarkable change can not take place.Therefore, the present invention especially with handle to small part heavy oil, promptly the FCC apparatus of long residuum or vacuum residuum is relevant.
In addition, the contriver finds unexpectedly and can not carry out under any pretreated situation successfully with the marine oil cracking.Because pre-treatment may be expensive, this is important and exceeds the advantage that those skilled in the art expect.Untreated marine oil may comprise multiple potential catalyzer poison and can influence the cracked undesirable substance.
Therefore,, the invention provides the method for preparing the biogasoline component, comprising from an aspect:
(I) obtain at least a bio oil, fish oil for example, if necessary, with this bio oil component liquefaction;
(II) with this bio oil of liquid state together with at least a mineral oil, for example comprise the mineral oil of heavy metal, add FCC apparatus together;
(III) will add the component cracking of described FCC apparatus, to form biological fluid liquefied oil gas (bioLPG) cut and biological naphtha fraction at least;
(IV) at least a portion alkylation or catalyzed polymerization that should the biology liquid petroleum gas cut; And
(V) at least a portion of the product of step (IV) and at least a portion of described biological naphtha fraction are merged, to form the biogasoline component.
On the other hand, the invention provides the method for preparing the biogasoline component, comprising:
(I) obtain at least a marine oil, if necessary, this marine oil is melted and it is in a liquid state;
(II) with this marine oil of liquid state together with at least a mineral oil, for example comprise the mineral oil of heavy metal, add FCC apparatus together;
(III) will add the component cracking of described FCC apparatus, to form biological naphtha fraction at least as the biogasoline component.
From more on the one hand, the invention provides the biogasoline that comprises by the biogasoline component of method for preparing.
From another aspect, the invention provides the purposes of the marine oil that is used for forming biogasoline.
Biogasoline is meant the gasoline that includes the biogenetic derivation component.Method of the present invention provides the biogasoline component.This component can be added into other biogasoline or abiotic component to form biogasoline, and perhaps self promptly can be used as biogasoline.
Petroleum naphtha is meant and comprises the cracking material cut that boiling point is up to 221 ℃, has the hydrocarbon polymer of 5 or 5 above carbon atoms (C5+).The biolith cerebrol is the biological components that comprises petroleum naphtha.
LPG (liquefied petroleum gas (LPG)) is meant the hydrocarbon polymer with 3 or 4 carbon atoms, for example propane, propylene, butane and butylene.BioLPG is the biological components that includes LPG.
Dry gas is meant hydrogen and has the hydrocarbon polymer of 1 or 2 carbon atom, for example methane, ethane and ethene.
Marine oil is meant the oils from oceanic resources, and described oceanic resources are for example fish, the marine alga of cultivating in pond or bio-reactor, small marine organisms (krill etc.) or for example marine mammal such as sea dog.In a preferred embodiment, described marine oil is a fish oil.Though preferably described marine oil is from marine organism, in the present invention, this term of marine oil also is used for comprising the fish oil of fresh water sources.
Bio oil used in this invention can be vegetables oil, animal oil or marine oil, and can obtain from any suitable source.These materials are easy to obtain.Suitable vegetables oil comprises vegetable oil (soya-bean oil, rapeseed oil), fruit oil (sweet oil) or the grease of plant such as Sunflower Receptacle for example.Animal oil can be from ox or pig or the like.Yet this oil is preferably from oceanic resources, for example sea dog, marine alga, krill, perhaps particularly fish, especially marine fishes.
Certainly, in cracking process, can use the mixture of bio oil.Can use the mixture of two kinds of different vegetables oil or vegetable oil is mixed with marine oil.
Bio oil also can be classified according to its free fatty acids (FFA) content.Preferably, the FFA content range that is used for bio oil of the present invention is 1.5-40%, and for example 2-30% is in particular 5-20%.
The bio oil that adds FCC apparatus need be in a liquid state.If this bio oil (or mixture of bio oil) is in a liquid state, can be without any pre-treatment with its direct adding.Yet some bio oil may be solid-state, therefore needs liquefaction before adding FCC apparatus, for example melts before adding FCC apparatus.Thawing can obtain simply by oil being heated to more than its fusing point (can about 50-60 ℃).
An advantageous feature of the present invention is, except possible thawing step, when bio oil is marine oil at all without any need for pre-treatment.Therefore after it is separated from marine organism, can under unprocessed state, directly use.It is very unexpected that charging be need not pre-treatment, because the marine oil of natural generation may be impure, this may be harmful to the FCC process.
This bio oil is added FCC apparatus together with at least a mineral oil component.The mineral oil component is meant the cut of crude oil.Preferred described mineral oil is gas oil (gas oil), for example straight run gas oil, vacuum gas oil, coker gas oil, long residuum, vacuum residuum and the residue oil fraction that produced by other purifying method.
Mineral oil and bio oil can be added FCC apparatus from pipeline separately, perhaps can mix making it enter FCC apparatus more earlier, in a kind of embodiment in back, preferably after any thawing step, mix.
In most cases bio oil is more less than mineral oil sulfur-bearing, if particularly mineral oil contains for example heavy oil component such as normal pressure or vacuum residuum.Like this, the mixture of bio oil and mineral oil probably than the sulfur-bearing of mineral oil own still less.As a result, can reduce the level of sulphur in the crackate, be necessary sulphur removal less in the sulphur removal operation in FCC apparatus downstream.
In most cases, bio oil also contains still less nitride than mineral oil, if particularly mineral oil contains for example heavy oil component such as normal pressure or vacuum residuum.Therefore the mixture of bio oil and mineral oil can contain still less nitride than mineral oil itself.Basic nitrogen compound is the main source of FCC apparatus oxynitride (NOx) discharging, and along with the minimizing of charging neutral and alkali nitride, the discharging of oxynitride also can reduce.In addition, known basic nitrogen compound can cause FCC catalyzer reversibility inactivation, and along with the minimizing of charging neutral and alkali nitride, the inactivation of catalyzer also can reduce.
The all biological oil ingredient can change in the scope of broad with respect to the relative consumption of mineral oil, and can depend on the raw-material availability of bio oil.Though therefore it is contemplated that and adopt many different oil ratioes to make useful biogasoline component, on commercial applications, with respect to mineral oil, the consumption of bio oil may be 50wt% or lower, be preferably 20wt% or lower, for example 15wt% or lower is in particular 10wt% or lower.Can use the minimum quantity of 1wt%.
For example black mineral oil such as normal pressure or vacuum residuum typically contains metal.Main metal pollutant is nickel (Ni) and vanadium (V), but black mineral oil also typically contains a small amount of other metal, for example calcium (Ca), potassium (K), iron (Fe), copper (Cu), sodium (Na) etc.
Metal concentration in the black mineral oil charging can be different and totally different according to the source of this charging, but the concentration of nickel and vanadium is usually up to 100ppm.The contriver determines nickel that modern FCC catalyzer can be tolerated and vanadium concentration at least up to 10ppm, and can not produce catalyst deactivation or other counter productive of unacceptable level.
Marine oil also comprises heavy metal, because heavy metal is the natural constituents of marine oil.The contriver recognizes that the metal and those metallographic phase that typically is present in the mineral oil that typically are present in the marine oil are same.The contriver further recognizes the metal concentration that typically is present in the marine oil, is the identical order of magnitude with the metal concentration that exists in the heavy oil that is suitable for catalytic cracking.Therefore, marine oil being added FCC apparatus with mineral oil, is negligible to the influence of the amount of heavy metal.The therefore definite FCC process of contriver will be moved well, and does not have catalyst deactivation.
Being operating as of FCC apparatus is known in the art, and implements in worldwide, only briefly sets forth at this.
Catalytic cracking is that petroleum refining industry is current, widely used method, is used for high boiling relatively heavy oil conversion is more valuable more lower boiling product, comprises gasoline and for example kerosene, Aviation Fuel and heating wet goods middle distillates.The charging of preheating is contacted with the cracking catalyst that is finely powdered of heat, and for producing the ideal cracking reaction, the granularity of catalyzer is generally 10-300 μ m.Usually catalyst temperature is about 500-550 ℃.Feeding temperature can be about 200 ℃, although in the present invention, with the temperature of bio oil charging remain on may cause that bio oil is degraded in some way or the temperature of reacting under be important.
During cracking, sedimentation of coke is on catalyzer, and this causes active and optionally forfeiture.By constantly the catalyzer of inactivation being taken out from cracking case, and in revivifier by contact its oxidation regeneration with air, thereby the removing coke.The burning of coke not only can be removed coke, and can be used for catalyzer is heated to the temperature that is suitable for cracking reaction.Catalyzer constantly circulates, and delivers to revivifier from reactor, again Returning reactor.Usually use zeolite catalyst.
As mentioned above, some bio oil, particularly marine oil include the deleterious heavy metal of zeolite catalyst.The contriver recognizes, handles the FCC catalyzer that can tolerate a certain amount of heavy metal to the FCC apparatus of small part heavy oil (being long residuum or vacuum residuum) in use.Therefore cracking will take place in marine oil under the situation that does not have serious catalyst activity forfeiture.
The cracking mixture that leaves FCC apparatus reaches separation column, is separated into multiple cut at separation column, comprises bioLPG and biolith cerebrol.Being operating as of separation column is known in the art, and implements in the refinery in the whole world.Therefore those skilled in the art will know that how to operate this tower.
Depend on the character of bio oil and mineral oil charging, the number change of formed every kind of cut is very big, forms the biological naphtha fraction of 30wt% at least but be preferably in the cracking material, more preferably 40wt% at least.
Be preferably and in the cracking thing, form the bioLPG cut of 10wt% at least, more preferably 15wt% at least.
Other component in the cracking thing and cut comprise water, carbonic acid gas, carbon monoxide, dry gas, LCO (light cycle oil) and HCO (heavy cycle oil).
Therefore recognize that the catalytic cracking meeting of bio oil produces the water of significant quantity, and the catalytic cracking of mineral oil charging can not.The contriver recognizes that under normal operation the water in the FCC apparatus is rendered as stripping tower steam, is lift gas in some cases, and in some cases as in separation column, removing salification.Therefore the water that is generated by the bio oil catalytic cracking can not cause any technologic problem.
The contriver further recognizes, can produce carbon monoxide and carbonic acid gas when the cracking bio oil.When cracking mineral oil, these components can not appear in the FCC product, and only can appear in the regenerator off-gas.The contriver is surprised to find, and has under the situation of these materials existence, and the cracking reaction meeting advances and can not lose activity.Though carbonic acid gas can be discharged in the environment, CO has height toxicity and must be handled before discharging.The contriver recognizes to burn by the dry gas that carbon monoxide is generated with cracking reaction and solves this problem.So the CO of all existence all can be converted into CO 2
In the step (IV) of method of the present invention, at least a portion in the bioLPG component that forms in cracking is that biological alkylide or catalyzed polymerization are biological polymer by alkylation, and this can be used in the biogasoline.
Alkyl turns to the method for knowing, and wherein, low-molecular weight compound (being preferably n-butene) under the situation that for example catalyzer such as hydrofluoric acid or sulfuric acid exists, is mixed with Trimethylmethane.Its product is known as alkylide, is made up of the mixture of high-octane branched paraffin.Because its aromatic substance and sulphur content are low, low and octane value (RON (research octane number (RON)) and MON (the motor-method octane number)) height of Reid vapour pressure (RVP), alkylide is the premium motor fuel blending stock.For example, octane-iso combines generation by butylene with Trimethylmethane, is defined as octane value 100.Other product is arranged, so octane value can respective change in alkylide.By the alkylation of bioLPG cut, formed the biogasoline mediation component that can significantly increase gasoline octane rating.
As alkylating alternative, can carry out catalyzed polymerization at least a portion bioLPG component.This comprise with two olefin hydrocarbon molecules for example butylene or propylene in conjunction with to form high-octane alkene blending stock.
No matter alkylation or catalyzed polymerization, it is essential perhaps bioLPG being separated into the component that is suitable for alkylating component (C4 component) or catalyzed polymerization, no matter only has part bioLPG cut can obtain handling in this step under which kind of situation.Usually have only the olefin component of bioLPG can be converted into the biolith cerebrol, and according to the character of the bioLPG that generated, alkene can form 1/3rd to 2/3rds of bioLPG, is preferably 50%-66%.
In addition, often forming the propylene of partial L PG component, itself is exactly valuable alkene, and can separate from bioLPG and be used for polymerization, is converted into petroleum naphtha and be not used in.Therefore the present invention can provide biological propylene monomer and biological polypropylene material.
According to the character of the bioLPG that is generated, the bioLPG of 25-33% can be converted into the biolith cerebrol.
So treated LPG can be merged with the part biological of making in step (III) at least petroleum naphtha, be preferably and the merging of all biological petroleum naphtha, and be used for gasoline.What in this case, surpass 50wt% originally contains the bio oil charging and can be used in the Fuel Petroleum.Will be appreciated that biolith cerebrol/bioLPG mixture self can serve as gasoline, but more commonly, it is in harmonious proportion with gasoline from the refinery other parts and combines with component, for example combines with reformate or the isomer that catalytic reforming produces.
Find that unexpectedly the biogasoline that utilizes marine oil to combine and make with mineral oil has higher RON than independent mineral oil.This result is extremely important, because in order to satisfy engine specification and the emission request that upgrades, it is indispensable that the fuel oil of higher RON is just becoming on market.The RON of fuel oil is high more, means the requirement of mineral oil upgrading also low more.Believe since in the material increase of aromatic components caused the raising of RON.Compare the biogasoline component of method manufacturing of the present invention, its RON meeting high 0.5% or more with the biogasoline component that only forms by mineral oil.
Biogasoline of the present invention is preferred for ground vehicle, but not aircraft.
In order to use more biomaterial, the biological LCO component in the cracking material can be used for biofuel.LCO is meant the cut of boiling point between 221-344 ℃, therefore is fit to be directly used in diesel oil.
Description of drawings
Fig. 1 has shown that MAT (micro-activity test) tests the content of the aromatic essence in the naphtha fraction that draws and the mutual relationship of transformation efficiency.
Fig. 2 shown turnover ratio that the test of the small-sized riser tube of FCC draws and the agent-oil ratio (catalyst-to-oil ratio) of the different mixtures that constitutes by FCC charging and fish oil between mutual relationship.
Fig. 3 has described the technical process of simplifying.Mineral oil mixes by conduit (1) with bio oil.In preheating (2) afterwards, the blended charging enters FCC apparatus (3).The cracked mixture is separated into biolith cerebrol in the conduit (5) and the bioLPG in the conduit (6) by separation column (4).BioLPG alkylation in device (7), and mix with selectively hydrotreated biolith cerebrol in installing (8).The mixture that generates forms the biogasoline component.Optionally, biological LCO is separated to conduit (9) from separation column (4).This biology LCO is hydrogen treatment in device (10) selectively, and can be as biofuel mediation component.
Embodiment
Now present invention is described in conjunction with following non-limiting example and accompanying drawing:
The catalytic cracking of fish oil among the embodiment 1:MAT
The cracking of demonstration fish oil in micro-activity test (MAT) reactor.The MAT test is the method that the catalytic cracking field is known.
Fish oil is from Norway Scanbio obtain, be equivalent to so-called crude fish oil, promptly do not carry out purified fish oil.Some characteristics of this fish oil are as shown in table 1:
Table 1: the characteristic of crude fish oil
Density, kg/l sulphur, the wt% total nitrogen, wt% Conradson carbon residue, the wt% total acid value, mg KOH/g Nian Du @100C, cSt Ca (ppm) Mg (ppm) K (ppm) Na (ppm) Cr (ppm) Mn (ppm) Ni (ppm) Zn (ppm) Al (ppm) Ba (ppm) Co (ppm) Cu (ppm) Fe (ppm) V (ppm) P (ppm) charging distillation type initial boiling point, ℃ 10% recovered temperature, ℃ 30% recovered temperature, ℃ 50% recovered temperature, ℃ 70% recovered temperature, ℃ 90% recovered temperature, ℃ final boiling point, ℃ ??0.9270??0.004??0.01??1.1??24.3??7.5??23??2.3??3.8??6.2??＜0.1??＜0.1??＜0.1??1.6??0.2??＜0.1??＜0.1??0.3??6.2??＜0.1??67??SIMDIST??36??60??335??342??380??400??466
In MAT test, test and compared two kinds of different chargings
The FCC charging (long residuum) that does not add fish oil
The fish oil that does not add the FCC charging
The FCC charging that is used in this test is the North Sea long residuum with following characteristic
Table 2: the characteristic of long residuum
Density 09275kg/l
Conradson carbon residue content 3.0wt%
Sulphur 0.404wt%
Ni????????????????1.6ppm
V?????????????????2.0ppm
Na????????????????0.6ppm
N (alkalescence) 420ppm
The NEKTOR766ST of FCC catalyzer that in this test, uses for providing by GRACE Davison, a kind of catalyzer of the metal that in design tolerable FCC charging, exists.Circulation propylene decatize (Cyclic Propylene Steaming) (795 ℃, 1400ppm Ni, 2200ppm V) is used for before test catalyst deactivation.
In same conversion (77.5%) contrast down, the interpolation productive rate of test gained is presented in the table 3:
Table 3: the productive rate of variant production and product cut (wt%)
Fish oil per-cent (%) in the charging ??0 ??100
Transformation efficiency ??77.5 ??77.5
??C 2- ??3.32 ??5.20
??C 2-(remove CO and CO 2In addition) ??3.32 ??3.24
??H 2O ??3.19
??LPG ??15.22 ??12.87
Petroleum naphtha ??50.13 ??47.09
??LCO ??15.20 ??16.56
??HCO ??7.30 ??5.94
Coke ??8.84 ??9.16
??RON ??87.9 ??90.9
As shown in table 3, when with the fish oil cracking, because CO and CO 2Formation, dry gas (C 2-) gain in yield.And can form water.As a result, the productive rate of LPG and petroleum naphtha descends.Because the petroleum naphtha aromaticity increases, the octane value of petroleum naphtha, promptly RON increases (in addition referring to Fig. 1).
In a specific refinery, constituted 44% of the material that is used for forming Fuel Petroleum from the naphtha fraction of FCC apparatus.For the total amount that makes the biotic component in the gasoline reaches 2%, suppose not have available biological polymer or biological alkylide, it is necessary sneaking into about 5.1% fish oil in the charging of FCC apparatus.
Based on the result of table 3, table 4 provides when sneak into the fish oil of 5.1wt% in FCC charging (long residuum) after, the change profile that FCC product component is estimated.
Table 4: the yield structure comparison of in the FCC charging, sneaking into the fish oil of 5.1wt% and in the FCC charging, not sneaking into fish oil
Fish oil (%) ??0 ??5.1 ??Δ
??C 2- ??3.32 ??3.42 ??0.10
??C 2-(remove CO and CO 2In addition) ??3.32 ??3.32 ??0.00
??H 2O ??0.16 ??0.16
??LPG ??15.22 ??15.10 ??-0.12
??C 3 ??5.95 ??5.96 ??0.01
??C 4 ??5.93 ??5.80 ??-0.13
??C 4 ＝ ??3.33 ??3.34 ??0.01
Petroleum naphtha ??50.13 ??49.97 ??-0.15
??LCO ??15.20 ??15.27 ??0.07
??HCO ??7.30 ??7.23 ??-0.07
Coke ??8.84 ??8.85 ??0.02
??RON ??87.9 ??88.1 ??0.15
As table 4 as seen, if handle a small amount of fish oil, during promptly about 10% or preferably even less than 10%, for example about 5% fish oil, expection only has small productive rate to change.
Embodiment 2 fish oil and the catalytic cracking of long residuum mixture in small-sized riser tube
In the small-sized riser tube of FCC of operation continuously, tested the different mixtures of two kinds of chargings (fish oil and North Sea long residuum) of embodiment 1 description.
The FCC catalyzer that uses in these tests is the equilibrium catalyst (ECAT) from the FCC apparatus of handling North Sea long residuum.
Fig. 2 has shown the mutual relationship of transformation efficiency with the agent-oil ratio of the different mixtures that is made of fish oil and FCC charging.As shown in the drawing, fish oil is sneaked into the FCC charging transformation efficiency is had no significant effect.
In same conversion (72.5%) contrast down, the interpolation productive rate of test gained is presented in the table 5.
Table 5: the productive rate of variant production and product cut (wt%)
Figure G2008800162117D00121
As table 4 was done, this result was used to estimate the yield structure when 5.1% fish oil is sneaked into the FCC charging.These results are presented in the table 6.
Table 6: based on the result of small-sized riser tube, the yield structure comparison of in the FCC charging, sneaking into the fish oil of 5.1wt% and in the FCC charging, not sneaking into fish oil
Figure G2008800162117D00122
As shown in table 6, when use small-sized riser tube as a result the time, if handle a small amount of fish oil, during promptly about 10% or be preferably even less than 10%, for example about 5% fish oil, expection only has small productive rate to change.

Claims (12)

1. method for preparing the biogasoline component, this method comprises:
(I) obtain at least a bio oil, if necessary, with this bio oil component liquefaction;
(II) this bio oil with liquid state adds fluidized catalytic cracker together with at least a mineral oil;
(III) will add the component cracking of described fluidized catalytic cracker, to form biological liquid petroleum gas cut and biological naphtha fraction at least;
(IV) at least a portion alkylation or catalyzed polymerization that should the biology liquid petroleum gas cut; And
(V) at least a portion of the product of step (IV) and at least a portion of described biological naphtha fraction are merged, to form the biogasoline component.
2. the method for claim 1, wherein described bio oil is a marine oil.
3. the method as claimed in any one of the preceding claims, wherein, described mineral oil comprises heavy metal.
4. the method as claimed in any one of the preceding claims, wherein, described bio oil has constituted the 10 weight % at the most of the component that adds described fluidized catalytic cracker.
5. method as claimed in claim 2, wherein, used described marine oil is without pre-treatment.
6. the method as claimed in any one of the preceding claims, wherein, described biological naphtha fraction constitutes at least 40 weight % of cracking material.
7. the method as claimed in any one of the preceding claims, wherein, described biological liquid petroleum gas cut constitutes at least 10 weight % of cracking material.
8. the method as claimed in any one of the preceding claims, wherein, described biological liquid petroleum gas cut is by alkylation.
9. the method as claimed in any one of the preceding claims, wherein, at least 50 weight % that contain in the charging of bio oil are converted into the biogasoline component.
10. method for preparing the biogasoline component, this method comprises:
(I) obtain at least a marine oil, if necessary, with this bio oil component liquefaction;
(II) with this marine oil of liquid state together with at least a mineral oil, for example contain the mineral oil of heavy metal, add fluidized catalytic cracker together; With
(III) will add the component cracking of described fluidized catalytic cracker, to form biological naphtha fraction at least, as the biogasoline component.
11. contain biogasoline by the biogasoline component of previously described method preparation.
12. marine oil is used to form the purposes of biogasoline.
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