CN101503638A - Process to produce clean gasoline/bio-ethers using ethanol - Google Patents

Process to produce clean gasoline/bio-ethers using ethanol Download PDF

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CN101503638A
CN101503638A CNA2009100096770A CN200910009677A CN101503638A CN 101503638 A CN101503638 A CN 101503638A CN A2009100096770 A CNA2009100096770 A CN A2009100096770A CN 200910009677 A CN200910009677 A CN 200910009677A CN 101503638 A CN101503638 A CN 101503638A
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fuel
blending
ethanol
gasoline
described method
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CN101503638B (en
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熊毅刚
凯丽·L·罗克
阿维德·尤德齐斯
米切尔·E·勒舍尔
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Catalytic Distillation Technologies
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Catalytic Distillation Technologies
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A fuel or fuel blendstock comprising ethanol, ethyl ethers, olefins, and alkanes. In some embodiments, the fuel or fuel blendstock of claim 1, wherein the fuel or fuel blendstock may have an octane number greater than 92 (RON+MON)/2). In other embodiments, the fuel or fuel blendstock may have a Reid vapor pressure less than 7.2 psi. Also disclosed is a process for the production of a fuel, the process including: contacting ethanol and at least one gasoline fraction including alkanes and olefins in the presence of a catalyst to form a fuel mixture including ethyl ethers, alkanes, unreacted olefins, and unreacted ethanol; and recovering the fuel mixture for use as a gasoline or gasoline blendstock without separation of the ethanol from the fuel mixture.

Description

Use improving one's methods of alcohol production clean gasoline/bio ether
Technical field
Embodiment disclosed herein relates generally to the act as a fuel method of component of renewable resources such as ethanol of using.In yet another aspect, embodiment disclosed herein relates to a kind of fuel composition that comprises alkane, alkene, ethanol and ethyl ether.More specifically, embodiment disclosed herein relates to the various chemistry of ethanol and gasoline fraction and the methods of injection (splash) blending of being used for.
Background technology
Fuel production merchant is standing to use the pressure of renewable resources as the blending raw material just more and more.Ethanol is mentioned frequently as the main example of this material.Among all renewable compounds of easily producing, ethanol is best suited in the gasoline.In fact, can become to rely on the modifier in straight alcohol and the fuel system to move engine design.
For whole economy, alcoholic acid uses the independence that can improve energy.This is because almost can be in the agricultural of the production Anywhere carbohydrate resource of the food of can growing.In addition, this production system has increased the social benefit that the economic surplus (surplus) that some transportations are relevant is transferred to the Rural areas.
The direct method that ethanol is blended in the gasoline is by mixing or " spraying blending ".In the United States Patent (USP) 6,258,987 (' 987) this method is being disclosed for example.Mixing the place,, comprising that the petroleum naphtha, reformate, virgin naphtha, isomerate, alkylide etc. of catalytic pyrolysis mix with the alcohol of aequum the various low product (subgrade) that wait of gasoline.The blending place is preferably the contiguous geographic position of distributing gasoline on (1) geography; (2) on the geography away from the low position of waiting the place of product of preparation.Resulting concoction is delivered in the element such as pipeline, railcar, tanker truck or barge of suitable storage facilities such as storage tank or distribution system.
Blending alcoholic acid different methods is by " chemistry blending ".In this case, ethanol is supplied in the refinery itself, and be covalently bound in the base gasoline.For example, United States Patent (USP) 5,633,416 grades have been described and have wherein been made C 1To C 4But alcohol and the low method that waits the etherificate olefine reaction in the product of gasoline.For example, can make ethanol and isobutene reaction to form Ethyl Tertisry Butyl Ether (ETBE).
Using chemistry or spraying the major advantage of concocting is to have improved the octane quality.Increase to the demand of more unleaded octane quality more and more needs high-grade fuel.In table 1, provided the blending value of the various oxidation resultants (oxygenates) in typical white gasoline.As can be seen, the octane value of ethanol and ETBE ((research octane number (RON) (RON)+motor-method octane number (MON))/2) is in the scope of 109-113.
Table 1
The oxidation resultant Octane Reid Vapour Pressure (psi)
Methyl alcohol 116 61
Ethanol 113 21.5
MTBE 106-110 8-9.3
ETBE 109-113 4-6
Although use ethanol to have many advantages as spraying the blending raw material, ethanol is blended into does not also have launched machine fuel industry in the gasoline, comprises petroleum refining industry, common transport pipe and car manufactures, acceptance easily.Diminish ethanol received basic problem on refinery operation and sales level and comprise that ethanol is the blending agents of not producing in the refinery place usually; Described in ' 987 patents, the blending place is usually away from refinery (that is, the ethanol that must produce near the Midwest in the corn place of production makes up with the gasoline of producing at Gulf Coast).
In addition, the blending of ethanol-hydrocarbon need remove from refinery or blending place oil depot and product delivery system and anhydrate, and reason is that the ethanol complete miscibility is in water.And the sale of ethanol concoction is restricted usually, because they are not accepted by all oil companies.In addition, pipeline may not accepted the ethanol concoction, reason be water potential may with relevant corrosion.On environment, ethanol may increase volatile organic and learn product (VOC) discharge, and does not reduce poisonous substance and NO effectively with ether as ETBE xDischarge.
Another serious problems relevant with the injection of ethanol blending relate to gasoline volatilization.As an example, the refiner must be reduced to about 0.8psi to 7.2psi at the Reid Vapour Pressure (RVP) of southern summer grade gasoline with them.As record in the table 1 is that ethanol has the Reid Vapour Pressure more much higher than ETBE.Therefore, under blending alcoholic acid situation, must produce low product or the blending raw material of waiting of special gasoline that the ethanol that is applicable in terminal sprays blending.This is special low RVP material, is therefore using ethanol to spray blending with after reaching 10 volume %, and the ethanol blending fuel of gained will have the RVP of regulation.Owing to removed C 4And C 5Compound, the ethanol concoction of the adjusting RVP of gained has lower octane value usually, makes this concoction partly compensate by the alcoholic acid higher octane and satisfies the RVP specification.The D86 T5 and the T10 of the concoction of adjusting RVP are also much higher, and reason is to have removed C 4And C 5Compound.C 4And C 5Compound remove the reduction that also may cause available gasoline volume.
For the C that removes 4And C 5Compound also must find a way out, and this may cause at the extra capital equipment of refinery or increase the recirculation and the reprocessing of these compounds.Usually in 10 to 20 cents scope, this depends on geographical position and season in the Economic Stimulus of 1 gallon of butane in the absorption gasoline.The octane value of butane is attractive (92) equally, and as gasoline component, butane is than the high several blending values of common white gasoline (87-89 usually).For C 5The stimulation of compound is similar.The chemistry blending provides and has obtained C 4The method of some value of compound such as butane or iso-butylene.
Therefore, need using renewable resources such as alcoholic acid method to exist.The gasoline concoction thing that described method also should provide the octane quality to be improved, wherein said method can provide and be removed the C that thinks ethanol creation RVP " space " usually 4And C 5The outlet of compound.
Summary of the invention
In one aspect, embodiment disclosed herein relates to fuel or the blending of fuel raw material (fuel blendstock) that comprises ethanol, ethyl ether, alkene and alkane.In some embodiments, the fuel of claim 1 or blending of fuel raw material, wherein said fuel or blending of fuel raw material can have the octane value (RON+MON)/2 greater than 92).In some embodiments, described fuel or blending of fuel raw material can have the Reid Vapour Pressure less than 7.2psi.
In yet another aspect, embodiment disclosed herein relates to a kind of method that is used to produce fuel, described method comprises: in the presence of catalyzer, ethanol is contacted with at least a gasoline fraction that comprises alkane and alkene to form fuel mixture, and described fuel mixture comprises ethyl ether, alkane, unreacted alkene and unreacted ethanol; With, from described fuel mixture, do not isolating under the alcoholic acid situation, reclaim described fuel mixture to be used as gasoline or gasoline blend.
From following description and appended claim, others and advantage will be tangible.
Description of drawings
Fig. 1 is being used to produce and comprising chemistry blending and spray the alcoholic acid fuel of blending or the simplification process flow sheet of fuel element according to an embodiment disclosed herein.
Fig. 2 is the simplification process flow sheet that is used to produce the alcoholic acid fuel that comprises chemistry blending and injection blending according to an embodiment disclosed herein.
Fig. 3 is the simplification process flow sheet that is used to produce the alcoholic acid fuel that comprises chemistry blending and injection blending according to another embodiment disclosed herein.
Embodiment
In one aspect, embodiment disclosed herein relates to the act as a fuel method of component of renewable resources such as ethanol of using.In yet another aspect, embodiment disclosed herein relates to a kind of fuel composition, and this fuel composition comprises alkane, alkene, ethanol and ethyl ether.More specifically, embodiment disclosed herein relates to the various methods that ethanol and gasoline fraction carry out chemistry and spray blending that are used for.
In some embodiments, in the presence of catalyst for etherification, ethanol is contacted to form fuel mixture with the gasoline fraction that comprises alkene, this fuel mixture comprises ethyl ether, alkane, unreacted alkene and unreacted ethanol.Can from fuel mixture, not isolate under the alcoholic acid situation then, fuel mixture is being reclaimed to be used as gasoline or gasoline blend.With contacting of catalyst for etherification can be in catalytic distillation tower and fixed bed etherification reactor at least one in carry out.
As used in this, gasoline fraction comprises that (1) is suitable as the various refinery streams of gasoline with the blending raw material; And/or flow by the blended gasoline that the two or more stream blending that will be suitable as gasoline blend separately forms (2).When gasoline blend that is fit to and the blending of other refinery stream, it generates the mix flow that satisfies the requirement of gasoline, and these requirements to gasoline have sufficient record in the regulations of federal and state.
The charging of disclosed method can comprise one or more ebullient petroleum fractionss in the gasoline boiling range in this article, comprises FCC gasoline, coking pentane/hexane, coking naphtha, FCC petroleum naphtha, straight-run spirit and comprises the two or more mixture of these streams.These gasoline concoctions stream typically has the normal boiling point in the scope of 0 ℃ and 260 ℃, and this normal boiling point is by ASTM D8 determination of distillation.Such charging comprises typical boiling range and is about C 6Light naphthar to 165 ℃ (330 ℉); Typical case's boiling range is about C 5Full range (full range) petroleum naphtha to 215 ℃ (420 ℉), ebullient heavy naphtha fraction more in the scope of about 125 ℃ to 210 ℃ (260 ℉ to 412 ℉), or about in or at least in 165 ℃ to 260 ℃ (330 ℉ to 500 ℉), ebullient heavy naphtha in preferred about 165 ℃ to 210 ℃ scope.Usually, Fuel Petroleum will distill in the scope of about room temperature to 260 ℃ (500 ℉).In some embodiments, can handle these streams to remove desulfuration, nitrogen and other unwanted component.
Being used for herein, the gasoline fraction of the embodiment of described etherification method can comprise C 3To C 9And higher hydrocarbon.For example, usually by fractionation separates refinery stream.Light naphtha fraction is a kind of such refinery stream, and because this cut comprises the very approaching compound of boiling point usually, it not is accurate therefore separating.Light naphthar refinery cut is as being used for by forming isoolefine (for example, the iC of ether with ethanol synthesis 5=and iC 6=compound) source is valuable.Therefore, for example, C 5Stream can comprise C 4C at the most 8, and high-grade compound more.These components can be saturated (alkane), unsaturated (monoolefine comprises isoolefine), and multifunctional unsaturated (for example diolefine).In addition, described component can be any or whole in the various isomerss of all cpds.Such mixture can easily contain 150 to 200 kinds of compounds.C 4To C 9Other hydrocarbon stream of carbon atom can disclosed in this article embodiment use.
In some embodiments, gasoline fraction can comprise C 4Cut, it can comprise C 3To C 5Or higher hydrocarbon (that is C, more 6+).In some embodiments, gasoline fraction can comprise C 5Cut, it can comprise C 4To C 8Or higher hydrocarbon more, comprise alkene.In some embodiments, gasoline fraction can comprise C 6Cut, it can comprise C 4To C 9Or higher hydrocarbon more, comprise alkene.In other various embodiments, gasoline fraction can comprise C 4, C 5, C 6And C 7+The mixture of one or more in the hydrocarbon, wherein this mixture comprises olefin(e) compound.Above-mentioned stream can comprise C 4To C 7Stream, gasoline fraction, FCC gasoline, coker gasoline and other refinery with similar performance flow.
For example, the saturated compound that comprises in the above-mentioned gasoline fraction can comprise the various isomerss of butane, the various isomerss of pentane and the various isomerss of hexane etc.For example, the olefin(e) compound that comprises in above-mentioned gasoline fraction can comprise iso-butylene and other butylene isomer, the various isomerss of amylene, the various isomerss of hexene and the various isomerss of heptene etc.In some embodiments, gasoline fraction can obtain from any source, but and can comprise the etherificate isoolefine that concentration is 1 to 45 weight %; Can comprise the isoolefine that concentration is 10 to 30 weight % in other embodiments; And in other embodiment again, can comprise the isoolefine that concentration is 15 to 25 weight %.
Other embodiment disclosed herein can be widely used in producing multiple ether by multiple different gasoline fraction.Can comprise tert-amyl ether, tertbutyl ether, uncle's hexyl ether and uncle's heptyl ether at the main ether that in method disclosed herein, produces.At etherification method is to be used to produce under the situation of method of butyl ether, and typical incoming flow is by the C that comprises Trimethylmethane, iso-butylene, normal butane, 1-butylene and 2-butylene 4The mixture of isomers is formed.In this method is to be used to produce under the situation of method of amyl ether, and the incoming flow component is included in 3-methyl-1-butene in the exemplary distribution of isomers, iso-pentane, 1-amylene, 2-methyl-1-butene alkene, Skellysolve A, trans-the 2-amylene, cis-2-amylene, neopentane and 2-methyl-2-butene.Although various sources can be used for the gasoline fraction that provides such, the most common source that is used for the incoming flow of these methods is from the light cracking hydrocarbon stream of FCC apparatus or comes the C of the water vapor cracking unit after comfortable divinyl extracts 4Stream.In one embodiment, the gasoline fraction that supplies in the methyltertiarvbutyl ether reactor can comprise isopentene, and it can comprise reactive isomers (2-methyl-1-butene alkene and 2-methyl-2-butene) and non-reacted isomers (3-methyl-1-butene) simultaneously.
The gasoline fraction that contains isoolefine can be mixed with ethanol, described ethanol can be from biological and petrochemical industry source.Preferably, ethanol is from biogenetic derivation, as the ethanol that is produced by corn or other farm crop.In some embodiments, the thinner that contains ethyl ether and gasoline fraction and ethanol can also be mixed as the recirculation flow that contains from the part of the product of methyltertiarvbutyl ether reactor.
Isoolefine in the mixture of gained and ethanol can be reacted on the catalyst for etherification that is fit to form ethyl ether.For example, this mixture is contacted with sulfuric acid macroporous ion exchange resin acid form, so that ethanol and isobutene reaction, thereby under situation, form ethyl ether with the highly selective that generates ether and the low yield that generates the isoolefine dipolymer.Be described in more detail below catalyst for etherification.
The methyltertiarvbutyl ether reactor effluent comprises ethyl ether, unreacted isoolefine and unreacted ethanol, and other component.Effluent can be reclaimed then with as fuel or blending of fuel raw material, and need not separating alcohol from fuel mixture.When for example using downflow boiling point reactors, the reactor effluent of at least a portion can be reclaimed to provide and contain ether thinner and temperature of reactor control.
Can reclaim the methyltertiarvbutyl ether reactor effluent then to be used as fuel or blending of fuel raw material.For example, the methyltertiarvbutyl ether reactor effluent can be recovered, store where necessary, and is transferred, to be used as fuel.In other embodiments, methyltertiarvbutyl ether reactor effluent and ethanol or other gasoline fraction injection blending wherein can be sprayed gained concoction storage and conveying to be used as fuel.
In some embodiments, gasoline fraction is transported to following blending place: vicinity distributes final alcohol blended fuel with the geographic blending place as fuel on the geography; With on the geography away from the blending place in place of preparation gasoline fraction.Can carry out a part of etherification of olefins in the blending place then.Can will contain the reactor effluent of ethanol and ethyl ether then as fuel or blending of fuel raw material.For example, then can be in described blending place, by mixing with alcohol or other gasoline fraction of aequum, preparation contains the fuel of ethanol and ethyl ether.
As mentioned above, can make isoolefine and alcohol reaction to form ether.The example of the ether that forms in the disclosed in this article embodiment can comprise: ethyl tert-butyl alcohol (ETBE), that is, and iso-butylene and alcoholic acid reaction product; Tertiary amyl ethyl ether (TAEE), that is, and isopentene and alcoholic acid reaction product and uncle's hexyl ethyl ether (THEE), that is, and various C6 isoolefine and alcoholic acid reaction product; Deng.
At first, show distillation column reactor system 5 according to some embodiments disclosed herein with reference to Fig. 1.The gasoline fraction 10 that contains isoolefine can be supplied in the distillation column reactor 12.The feed entrance point of gasoline fraction 10 can be higher than, be lower than and contain catalyst area 14 or in the centre that contains catalyst area 14.The ethanol synthesis that contained isoolefine can be supplied with via stream 15 in containing catalyst area 14 in hydrocarbon stream 10 is to produce ether.Distillation column reactor 12 can comprise reboiler 16 and overhead product system 17, and they provide the control to liquid in the distillation column reactor 12 and steam flow separately.
Can operate distillation column reactor system 5 by this way, make unreacted alcoholic acid at least a portion in hydrocarbon stream 10 more heavy hydrocarbon and owing to the ether that forms of reaction of alkene and alcohol, leave distillation column reactor 12 with the form of the bottomsstream stream 18.Can will comprise lighter hydrocarbons condensation in overhead product system 17 of alkane and some unreacted alkene, and reclaim, perhaps be recycled to the top of distillation column reactor 12 with the form that refluxes via pipeline 21 with the form of overhead product stream stream 20.
As shown, ethanol can be supplied in the distillation column reactor 12 with hydrocarbon stream 10, perhaps can supply to the different positions on the distillation column reactor 12, comprise the level of the feed points that is higher or lower than hydrocarbon incoming flow 10.Because the azeotropic mixture that can between ethanol and various hydrocarbon, form, and because selected operational condition, ethanol can be present in the bottomsstream stream 18 and the overhead product stream 20 simultaneously.Can not separate ethanol usually with containing the chemistry blending and spraying the alcoholic acid of concocting and flow 18 then as fuel or blending of fuel raw material.
In other embodiments, can other ethanol be joined in the distillation column reactor system in the position that is higher than the gasoline fraction charging.For example, ethanol can be joined top of tower, catalyst for etherification zone top, one or more in the catalyst for etherification zone or join the tower tray that is lower than the catalyst for etherification zone.By this way, the concentration of ethanol in the various piece of tower can be increased or is controlled to required level.
In some embodiments, hydrocarbon and pure charging can be passed through the fixed bed etherification reactor, thereby are ether with at least a portion feedstock conversion.United States Patent (USP) 5,003,124 and 4,950,803 disclose in the boiling point fixed-bed reactor C 4Or C 5Isoolefine and pure etherificate and oligomeric liquid phase process, described boiling point fixed-bed reactor are controlled in reaction mixture are remained under the pressure of its boiling point, and can be directly connected on the catalytic distillation reactor.Fixed-bed reactor can be homogeneous reaction device such as liquid phase or Gas-phase reactor, fixed bed boiling point reactors or their combination.In some embodiments, can be under the state of stream of pulses the fixed-bed operations boiling point reactors.
In some embodiments, the effluent from fixed-bed reactor directly can be used as fuel or blending of fuel raw material.In other embodiments, the effluent of autoreactor is transported to the catalytic distillation reactor assembly with further processing in the future then, wherein operates the catalytic distillation reactor assembly as mentioned above.
In other embodiments, the gasoline fraction that supplies in the methyltertiarvbutyl ether reactor can experience treatment step before entering the catalytic distillation reactor assembly.For example, various gasoline fractions can experience selective hydrogenation, hydrogenating desulfurization, hydrodenitrification and other method well known by persons skilled in the art of hydrotreatment, diene and/or acetylene.
With reference now to Fig. 2,, shows the simplified flow chart that is used to produce the method that contains alcohol fuel according to an embodiment disclosed herein.Make gasoline fraction separately or concoct each that raw material passes through intake pipeline 41,42,43,44,45 and 46.Although figure 2 illustrates 6 intake pipelines, be to be understood that and use more or less intake pipeline.Each root intake pipeline 41-46 is discharged in the blending chamber 47, wherein mixes the blending raw material and mixes to form the low product concoction that waits.Then, by in reactor 35 with via the ethanol synthesis of the aequum of pipeline 37 chargings and/or mix, can contain ethyl ether and alcoholic acid fuel or blending of fuel raw material with what hang down etc. that the product concoction is converted into required specification.Where necessary, can turn back in the reactor via fluid line 38 recirculation flows.
Resulting fuel or blending of fuel raw material are reclaimed from reactor 35 via export pipeline 48, and be sent in the element such as pipeline, railcar, tanker truck or barge of suitable storing device such as storage tank or distribution system (not shown).If desired, can add ethanol or other gasoline blend of other injection blending via pipeline 39.Each root among intake pipeline 37,39, the 41-46 can dispose relevant measuring apparatus, is controlled to required specification such as alcohol concn, oxygen level, Reid Vapour Pressure, octane value and other performance that is fit to the final composition with fuel.
Although the mixture with various gasoline blend shown in Figure 2 supplies in the methyltertiarvbutyl ether reactor, methyltertiarvbutyl ether reactor can be used for the specific cut of etherificate.Then, shown in Fig. 3, the gasoline blend of all the other cuts and etherificate can be concocted to required fuel specification, in Fig. 3, identical mark is represented identical parts.
According to embodiment disclosed herein, by above-mentioned chemistry and spray the octane value (motor method octane or (RON+MON)/2) of fuel that blending obtains or blending of fuel raw material can be greater than 90.In other embodiments, octane value can be greater than 91; In other embodiments, can be greater than 92; In other embodiments, can be greater than 93; In other embodiments, can be greater than 95; In other embodiments, can be greater than 98; And in other embodiment again, can be greater than 100.
According to embodiment disclosed herein, by above-mentioned chemistry and spray the Reid Vapour Pressure of fuel that blending obtains or blending of fuel raw material can be less than 7.5psi.In other embodiments, Reid Vapour Pressure can be less than 7.2psi; In other embodiments, can be less than 7psi; In other embodiments, can be less than 6.9psi; In other embodiments, can be less than 6.8psi; In other embodiments, can be less than 6.7psi; In other embodiments, can be less than 6.6psi; And in other embodiment again, can be less than 6.5psi.
The alcoholic acid fuel that comprises chemistry and injection blending disclosed herein or the oxygen level of blending of fuel raw material can be similar to the alcohol fuel that sprays blending.In some embodiments, the former oxygen level that can have at least 2 weight % of disclosed in this article fuel and blending of fuel; The oxygen level that can have in other embodiments, at least 2.25 weight %; The oxygen level that can have in other embodiments, at least 2.5 weight %; The oxygen level that can have in other embodiments, at least 2.75 weight %; The oxygen level that can have in other embodiments, at least 3.0 weight %; The oxygen level that can have in other embodiments, at least 3.25 weight %; And in other embodiment again, can have the oxygen level of at least 3.5 weight %.
As mentioned above, disclosed in this article fuel and blending of fuel raw material comprise the ethanol that sprays blending and chemistry blending simultaneously, and wherein the ethanol of chemistry blending is in the form of ether.Total ethanol content in fuel or the blending of fuel raw material, the ethanol that is included in the chemistry blending in the fuel mixture is at least 8 volume % interior; Be at least 9 volume % in other embodiments; Be at least 10 volume % in other embodiments; Be at least 11 volume % in other embodiments; Be at least 12 volume % in other embodiments; And be at least 15 volume % in other embodiment again.
Catalyst for etherification
Normally used any catalyzer can use in the disclosed in this article embodiment in etherification method.In each embodiment, can use conventional Zeo-karb and/or zeolite.Therefore, resin can contain sulfonic acid group, and polymerization or copolymerization that can be by aromatic vinyl compound, sulfonation subsequently and obtaining.The example that is applicable to the aromatic vinyl compound of preparation polymkeric substance or multipolymer comprises: vinylbenzene, Vinyl toluene, vinyl naphthalene, vinyl ethyl-benzene, vinyl toluene, vinyl chlorobenzene and vinyl-dimethyl benzene.By each aromatic ring, weak acid cation exchange resin can contain about 1.3 to 1.9 sulfonic acid group.In some embodiments, resin can be based on the multipolymer of aromatic monovinyl compound and the many vinyl compounds of aromatics, and wherein many vinyl benzenes content is about 1 to 20 weight % of multipolymer.In some embodiments, ion exchange resin can have about granularity of 0.15 to 1mm.Except that above-mentioned resin, can use perfluorinated sulfonic resin, perfluorinated sulfonic resin is the multipolymer of fluorosulfonyl vinyl ethyl and fluorocarbon.
The catalyzer that is used in etherification method disclosed herein is called as the zeolite of mesopore or ZSM-5 type in the time of can including.In other embodiments, zeolite can be the selectivity acid metal silicate zeolite that is selected from the middle hole shape among ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-50, the MCM-22, and the more zeolite Y and the zeolite beta of macropore.According to the technology of knowing in the art, for example by ion-exchange, the initial positively charged ion relevant with zeolite used herein can be replaced by multiple other positively charged ion.The typical positively charged ion that replaces comprises hydrogen, ammonium, alkylammonium and metallic cation and their mixture.Under the situation of metallic cation, the metal of IB to VIIIA family that can the life cycle table for example comprises iron, nickel, cobalt, copper, zinc, palladium, calcium, chromium, tungsten, molybdenum, rare earth metal etc.These metals can also exist with their form of oxide compound.
In other embodiments, the catalyst for etherification that is used for isoolefine comprises mineral acid such as sulfuric acid, boron trifluoride, the phosphoric acid on diatomite, phosphorus-modified zeolite, heteropolyacid and various sulfate resin.These resin type catalysts can comprise resol and vitriolic reaction product and comprise sulphonated polystyrene resin, comprise those sulphonated polystyrene resins with divinyl benzene crosslinked.Special catalyst for etherification be the sulfonic acid ion exchange resin of macropore acid form such as United States Patent (USP) 2,922, the sulfonated phenylethylene-divinylbenzene resin described in 822, it has about degree of crosslinking of 5 to 60%.Resin dedicated existing in the art the description, and comprise as United States Patent (USP) 3,489 the fluorosulfonyl vinyl ether described in 243 and the multipolymer of fluorocarbon.The resin of another kind of special preparation is by at United States Patent (USP) 4,751, the SiO that describes in 343 2The cationite of-modification is formed.The macroporous structure of the resin that is fit to is at United States Patent (USP) 5,012, has a detailed description in 031, and it has at least about 400m 2The mean pore size of the surface-area of/g, about pore volume of 0.6 to 2.5ml/g and 40 to 1000 dusts.According to expectation, present method can use the containing metal resin to carry out, and described containing metal resin contains from subgroup VI, the VII of periodictable or one or more metals of VIII, and as chromium, tungsten, palladium, nickel, chromium, platinum or iron, this is at United States Patent (USP) 4,330, and 679 have description.Can pass through with reference to United States Patent (USP) 2,480,940,2,922,822 and 4,270,929 obtain the further information about the catalyst for etherification that is fit to.
In some embodiments, catalytic distillation structure used herein comprises cation exchange resin particles is placed in a plurality of bag in the strap that this strap is subjected to by two Stainless Steel Wires are twisted with the fingers the support of the open cell mesh that weaves with volution together in the anti-reactor of distillation tower.Allow the necessary loss of flowing and preventing catalyzer like this.Described cloth can be any material of inert in reactor, as cotton, flax, fiberglass cloth or TEFLON.United States Patent (USP) 4,302,356,4,443,559 and 5,730,843 disclose the catalyst structure that can be used as distillation structure, and they are combined in this by reference.At for example United States Patent (USP) 5,190,730,5,231,234,5,248,836,5,292,964,5,637, other catalyst for etherification that is fit to has been described in 777 and 6,107,526 grades.
Embodiment
The character that has compared three kinds of fuel in table 2, described three kinds of ethanol that promptly are typical base gasoline, RVP regulate spray the gasoline of blending, and use having chemistry and spraying the alcoholic acid fuel of blending of method formation disclosed herein.For relatively,, RVP is kept constant in the influence of mensuration to octane (RON), and be determined at the amount that can produce every day in the typical method for three kinds of whole fuel.In addition, for containing alcoholic acid fuel, mixture further is restricted to has equal oxygen level.
Table 2
Performance Base gasoline The ETOH concoction that RVP regulates (spraying the ETOH of blending) The ETOH of chemistry+injection blending
RVP(psi) 6.45 6.45 6.45
RON 93.0 90.8 90.6
Proportion 0.7438 0.7618 0.7600
Oxygen (weight %) 0.0 3.7 3.7
Alkene (weight %) 38.9 31.8 30.0
The D86 distillation
T5(℉) 120 140 126
T10(℉) 128 161 155
T50(℉) 213 216 216
T90(℉) 326 327 325
Volume (bbl/ days) 100,000 (normalizings) 94,960 104,300
For the ethanol concoction of regulating RVP, regulate gasoline blend to produce the blending raw material that is applicable to ethanol injection blending by removing lighter fuel element, make final fuel satisfy the RVP specification.Owing to remove the C that satisfies the RVP specification 4And C 5Compound, promptly high-octane number component is sprayed the alcoholic acid RON that concocts and is lower than base gasoline.This reduction is partly compensated by the alcoholic acid high-octane rating.Because removing of lighting end, the amount of the gasoline of the injection that can get blending also is lower than conventional gasoline.
The alcohol fuel of chemistry and injection blending prepares to form ETBE and TAEE by making major part (～95%) inherent iso-butylene and reactive isopentene and ethanol synthesis.In addition, C 6The cut of isoolefine also is converted into C 6Ethyl ether.Other ethanol is sprayed blending so that basic oxygen level is at most 3.7 weight % then.Compare slightly reduction although RON sprays concoction with the ethanol of regulating RVP, available amount of gasoline is higher.In addition, generate the olefin(e) centent of chemistry blending advantageously reduction finished product fuel of ether.If the conventional basic regular price gasoline of refiner's hydrotreatment is to reduce olefin(e) centent, then chemical blending method may reduce required hydrotreatment.Therefore, compare with independent injection blending, alcoholic acid chemistry blending step and further injection blending can cause the income of significant amount of gasoline, and octane point barrelage (Octane-point-barrels).
As mentioned above, embodiment disclosed herein can provide alcoholic acid fuel and the blending of fuel raw material that comprises chemistry simultaneously and spray blending.Method disclosed herein can provide a kind of etherification method of simplification, wherein can eliminate the ethanol recovery part fully, thereby saves capital and running cost.
Advantageously, embodiment disclosed herein can provide at least one in following: be used for C 4The outlet of alkene; In addition be comprised in C in the fuel composition 4And C 5Hydrocarbon has effectively utilized the ethanol in clean fuel, reduces automobile emission simultaneously; On profit, be reduced in the alkene in the gasoline effectively.In addition, method disclosed herein can provide a kind of ethanol to spray the alternatives of blending.
By the ethanol chemistry being concocted and being sprayed the synergistic combination (for similar oxygen concn) that is blended in the clean gasoline, not only keep and use alcoholic acid economy, society and environmental benefit, and they are improved actually.By using method disclosed herein, can obtain the more gasoline amount, and use it, utilize more ethanol.Quality of fuel can be improved, and can reduce the C that must handle (re-run) in refinery again 4And C 5The amount of material.
Although kept the octane value of fuel, can under the situation of not hydrotreatment, significantly reduce alkene, so the hydrogen consumption of the limited refiner of alkene is 0.Therefore, can on refiner, produce the less total CO that satisfies the hydrogen demand and supply 2
Although the disclosure comprises a limited number of embodiments, have benefited from of the present disclosure it will be appreciated by those skilled in the art that and to design other embodiment that does not depart from the scope of the present disclosure.Therefore, described scope should only be subjected to the restriction of appended claim.

Claims (16)

1. fuel or blending of fuel raw material, described fuel or blending of fuel raw material comprise ethanol, ethyl ether, alkene and alkane.
2. described fuel of claim 1 or blending of fuel raw material, wherein said fuel or blending of fuel raw material have the octane value (RON+MON)/2 greater than 92).
3. described fuel of claim 1 or blending of fuel raw material, wherein said fuel or blending of fuel raw material have the Reid Vapour Pressure less than 7.2psi.
4. described fuel of claim 1 or blending of fuel raw material, wherein said fuel or blending of fuel raw material have the oxygen level of at least 3.5 weight %.
5. method that is used to produce fuel, described method comprises:
In the presence of catalyzer, ethanol is contacted with at least a gasoline fraction that comprises alkane and alkene, to form fuel mixture, described fuel mixture comprises ethyl ether, alkane, unreacted alkene and unreacted ethanol; And
From described fuel mixture, do not isolating under the alcoholic acid situation, reclaiming described fuel mixture to be used as gasoline or gasoline blend.
6. the described method of claim 5, wherein said contact comprises:
Ethanol and the gasoline fraction that comprises isoolefine are fed in the distillation column reactor system, and described distillation column reactor system comprises at least one etherification reaction zone; With
Described fuel mixture form with the bottomsstream cut from described distillation column reactor system is extracted.
7. the described method of claim 5, wherein said contact comprises:
Ethanol and the gasoline fraction that comprises isoolefine are fed in the fixed bed reactor system, and described fixed bed reactor system comprises at least one etherification reaction zone.
8. the described method of claim 5, described method also comprise at least a and described fuel mixture blending in the ethanol and second gasoline fraction.
9. the described method of claim 5, described method also comprise at least a in ethanol and the described gasoline fraction be transported to carries out described the contact and the place of recovery.
10. the described method of claim 5, wherein said conveying comprise uses at least a in pipeline, barge, tanker truck and the railcar.
11. the described method of claim 5, wherein said gasoline fraction comprises C 4To C 9Alkane.
12. the described method of claim 5, wherein said gasoline fraction comprises C 4To C 7Alkene.
13. the described method of claim 5, wherein said ethyl ether comprise at least a in Ethyl Tertisry Butyl Ether, tertiary amyl ethyl ether, uncle's hexyl ethyl ether and the uncle's heptyl ethyl ether.
14. the described method of claim 5, wherein said gasoline fraction comprises C 4Cut, C 5Cut, C 6At least a in cut and the light naphtha fraction.
15. the described method of claim 5, wherein said fuel mixture has the Reid Vapour Pressure less than 7.2psi.
16. the described method of claim 5, the oxygen level of wherein said fuel mixture is at least 3.5 weight %.
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