CN102811990B - Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels - Google Patents

Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels Download PDF

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CN102811990B
CN102811990B CN201180014151.7A CN201180014151A CN102811990B CN 102811990 B CN102811990 B CN 102811990B CN 201180014151 A CN201180014151 A CN 201180014151A CN 102811990 B CN102811990 B CN 102811990B
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ethanol composition
fuel
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composition
fuel ethanol
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CN102811990A (en
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V·J·约翰斯顿
L·萨拉戈
R·J·瓦尼尔
H·魏纳
G·格鲁森多夫
T·霍顿
R·耶夫蒂奇
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Celanese International Corp
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Priority claimed from US12/852,290 external-priority patent/US8460405B2/en
Priority claimed from US12/903,756 external-priority patent/US8541633B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • 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
    • 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
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    • 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
    • C10L1/1857—Aldehydes; Ketones
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

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  • General Chemical & Material Sciences (AREA)
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Abstract

A denatured fuel ethanol composition for blending with fuels, including gasoline and diesel fuel. The composition includes an ethanol composition comprising at least 92 wt.% ethanol; and from 95 wppm to 1,000 wppm isopropanol; and at least 1.96 vol. % fuel denaturant.

Description

For being used as the fuel ethanol composition of motor spirit with gasoline or diesel fuel blend
The cross reference of related application
The application is the U. S. application No.12/852 submitted on August 6th, 2010, part continuation application (the U.S. Provisional Application No.61/300 of this U.S. Application claims submission on February 2nd, 2010 of 290,815, with the U.S. Provisional Application No.61/332 that on May 7th, 2010 submits to, 696, the U.S. Provisional Application No.61/332 that on May 7th, 2010 submits to, 699; The U.S. Provisional Application No.61/332 that on May 7th, 2010 submits to, the U.S. Provisional Application No.61/346 that on May 19th, 728 and 2010 submits to, the right of priority of 344), and be the U. S. application No.12/903 submitted on October 13rd, 2010, part continuation application (the U.S. Provisional Application No.61/332 of this U.S. Application claims submission on May 7th, 2010 of 756, the U.S. Provisional Application No.61/300 that on February 2nd, 726 and 2010 submits to, the right of priority of 815), by reference their full content and disclosure are incorporated to herein.
Invention field
Present invention relates in general to produce and/or purifying for the production of the method for fuel ethanol, particularly fuel ethanol composition.
Background of invention
Ethanol is produced by petrochemical materials such as oil, Sweet natural gas or coal routinely, is produced by raw material midbody such as synthetic gas, or by starchiness material or cellulose materials such as corn (corn) or sugarcane production.By petrochemical materials and the acid-catalyzed hydration, the methyl alcohol homologization, directly alcohol synthesis and Fiscber-Tropscb synthesis that are comprised ethene by the ordinary method of cellulose materials production ethanol.The unstable of petrochemical materials price impels the conventional ethanol cost fluctuation produced, and when cost of material raises, this makes the needs in the alternative source to alcohol production larger than ever.By fermentation, starchiness material and cellulose materials are converted into ethanol.But the consumer that fermentation is generally used for fuel use or consumption ethanol is produced.In addition, the fermentation of starchiness or cellulose materials and food sources form compete and to for industrial use the amount of producible ethanol be applied with restriction.
About the ethanol using fermentation to produce, International Monetary Fund (InternationalMonetary Fund) observe in 2008 that such fuel accounts for this year global liquid fuel supply 1.5%, but represent the nearly half that food crop consumption increases, this is mainly owing to cause in the use of american corn base ethanol (corn-based ethanol).In 2011, the american corn crop of 40% will enter motor spirit.In addition, think that this fact serves effect in higher food prices.
Dehydrated alcohol or substantially anhydrous ethanol are often preferred for fuel applications.But dehydrated alcohol or substantially anhydrous ethanol are difficult to be obtained by conventional hydro and separation method usually.Such as, the second alcohol and water produced in conventional hydro reaction can form binary azeotrope.This azeotrope is containing 95% ethanol and about 5% water of having an appointment.Because the boiling point of this azeotrope (78 DEG C) is just slightly lower than the boiling point (78.4 DEG C) of straight alcohol, so be difficult to obtain anhydrous or anhydrous ethanol composition substantially by simple, conventional distillation by coarse ethanol composition.
The conventional ethanol composition formed by aforesaid method contains the impurity that must remove.Such as, U.S. Patent No. 5,488,185 utilize petrochemical materials and relate to containing the ethylene stream as the ethane of impurity or containing the flow of propylene as the propane of impurity, under hydration catalyst exists, described ethylene stream or the hydration of flow of propylene water vapour are produced ethanol or Virahol respectively.After shifting out alcohol, make gaseous product stream experience absorption, thus produce ethylene-rich stream or rich propylene stream.Ethylene-rich stream or rich propylene stream are recycled to hydration reactor.
U.S. Patent No. 5,185,481 and 5,284,983 relate to the common fermentation processes for the production of ethanol.The ethanol composition produced comprises impurity such as methyl alcohol, acetaldehyde, n-propyl alcohol, propyl carbinol, ethyl acetate, 3-methyl butanol, diethyl ether, acetone, sec-butyl alcohol and crotonic aldehyde.These reference also disclose the separation method with the extraction solvent process coarse ethanol aqueous solution comprising liquid carbon dioxide or the supercritical carbon dioxide.
U.S. Patent No. 5,445,716; 5,800,681 and 5,415,741 separation methods relating to the mixture of ethanol and Virahol.Be difficult to ethanol to be separated with Virahol by conventional distil-lation or rectifying, this is because their boiling point is close.Ethanol can be separated with Virahol easily through extractive distillation.Effective extraction agent is limonene, methyl-phenoxide and ethylbenzene.Mixture in these reference comprises the Virahol of significant quantity, the Virahol of such as at least 21.5wt.%.
In addition, U.S. Patent No. 5,858,031 method relating to the visibility improving the flame that moisture alcohol radical fuel composition produces during free combustion in atmosphere.Described fuel comprises the water of about 10%-30% volume, and the alcohol mixture of about 70%-90% volume (comprising ethanol and Virahol), and wherein ethanol accounts for the about 24%-83% volume of this fuel composition.The method comprises provides Virahol amount to be the fuel composition of about 7%-60% volume, and wherein in fuel, the volume ratio of Virahol and ethanol is no more than 2:1.
Although ordinary method can be produced and/or purifying ethanol composition, these methods depend on petrochemical materials or fermentation technique to produce ethanol composition.
Therefore, need not rely on petrochemical materials and do not use the method ethanol production that can be used for producing fuel ethanol composition of fermentation technique.
Summary of the invention
In one embodiment, the present invention relates to the fuel ethanol composition comprising ethanol composition and at least 1.96vol.% fuel denaturing agent.Ethanol composition comprises ethanol and Virahol.Preferably, ethanol composition comprises at least 92wt.% ethanol, and 95wppm-1,000wppm Virahol.Ethanol composition has high purity and can comprise one or more organic impuritys being less than 1wt.%.These organic impuritys can comprise such as acetaldehyde, acetic acid, diethyl acetal, ethyl acetate, n-propyl alcohol, butanols, 2-butanols, isopropylcarbinol and their mixture.Such as, ethanol composition can comprise and be less than 10wppm acetaldehyde, is less than 10wppm diethyl acetal (diethyl acetal), and/or is less than 300wppm C 4-C 5alcohol.In other embodiments, ethanol composition is substantially free of benzene, methyl alcohol and/or C 5alcohol.In other embodiments, this fuel ethanol composition comprises the water being less than 1vol.%.Fuel ethanol composition disclosed herein and gasoline or diesel fuel blend can be used as motor spirit.
In another embodiment, the present invention relates to the fuel ethanol composition comprising ethanol composition and at least fuel denaturing agent of 1.96vol.%.This ethanol composition comprises the ethanol of at least 95wt.% and the Virahol of at least 95wppm.In another embodiment, Virahol exists with the amount being less than 1000wppm.Preferably, ethanol composition also comprises acetaldehyde, and in ethanol composition, the amount of acetaldehyde is less than the amount of Virahol.As an example, acetaldehyde can exist by the amount being less than 10wppm.In another embodiment, ethanol composition also comprises n-propyl alcohol.Preferably, the weight ratio of Virahol and n-propyl alcohol is 1:1-1:2.Virahol can exist by the amount being less than 1000wppm and/or n-propyl alcohol can exist by the amount being less than 270wppm.In other embodiments, this fuel ethanol composition comprises the water being less than 1vol.%.This fuel ethanol composition and gasoline or diesel fuel blend can be used as motor spirit.
In another embodiment, the present invention relates to the fuel ethanol composition comprising ethanol composition and at least fuel denaturing agent of 1.96vol.%.Ethanol composition comprises at least 92wt.% ethanol and at least two kinds of optional other alcohol existed with the amount being less than 1wt.%.Described at least two kinds of other alcohol can be selected from n-propyl alcohol, Virahol, butanols, 2-butanols and isopropylcarbinol.In another embodiment, the one in described at least two kinds of other alcohol is Virahol and ethanol composition comprises at least 95wppm Virahol.Ethanol composition can comprise the Virahol of the amount being less than 1000wppm.Preferably, ethanol composition is substantially free of methyl alcohol.In other embodiments, this fuel ethanol composition comprises the water being less than 1vol.%.Fuel ethanol composition disclosed herein and gasoline or diesel fuel blend can be used as motor spirit.
Accompanying drawing explanation
Below with reference to the accompanying drawings describe the present invention in detail, wherein identical numeral indicates similar part.
Accompanying drawing 1 is the schematic diagram of hydrogenation system according to an embodiment of the invention.
Accompanying drawing 2 is schematic diagram of reaction zone according to an embodiment of the invention.
Accompanying drawing 3 is the coordinate diagram of the isopropanol content showing some conventional ethanol compositions.
Accompanying drawing 4A is the schematic diagram with the hydrogenation system of the 4th tower according to an embodiment of the invention.
Accompanying drawing 4B is the schematic diagram with the hydrogenation system of mol sieve unit according to an embodiment of the invention.
Detailed Description Of The Invention
As ASTM D4806 permit, " denaturing agent of permission " refers to natural gasoline, gasoline blending stock and white gasoline.
" denaturing agent " refers to that the formula ratified according to administration joins in ethanol makes it be not suitable for drinking thus one or more materials preventing from imposing beverage alcohol tax.
" diesel oil fuel " refers to C 9-C 24the mixture of hydrocarbon, described hydrocarbon comprises about 50vol.%-and is about 95vol.% aliphatic hydrocarbon (wherein about 0vol.%-is about 50vol.% is naphthenic hydrocarbon), about 0vol.%-is about 5vol.% alkenes, and about 5vol.%-is about 50vol. aromatic hydrocarbons, and boiling point is about 280 °F (138 DEG C)-750 °F (399 DEG C).
" natural gasoline " refers to that vapour pressure is between natural gas condensates and liquefied petroleum gas (LPG) and the natural gas liquids of boiling point in gasoline-range.Natural gasoline is liquid at ambient pressure and temperature, may be used for making ethanol sex change and for fuel ethanol be allow denaturing agent.
" gasoline blending stock " refers to the blending stock that usually can obtain in petroleum refinery.Such blending stock including, but not limited to alkylide stream, catalytically cracked gasoline stream (such as cracking naphtha); Aromatics saturated vapor oil flow, light straight-run spirit stream, heavy straight-run gasoline stream, dehexanizing column tower bottoms stream, dehexanizing column top stream, hydrocracking device topping light naphthar, reformate, toluene and butane stream.Alkylide stream to be usually polymerized with lower olefin compound such as butylene and propylene by Trimethylmethane and to obtain on an acidic catalyst (such as sulfuric acid, hydrofluoric acid or aluminum chloride).Catalytically cracked gasoline stream is produced by fluidized catalytic cracking unit (FCC) or thermocatalysis cracker (TCC) usually.Light and heavy straight-run gasoline stream is obtained by the air distillation of crude oil usually.Reformate streams usually by catalytic reforming so that petroleum naphtha (typically having low octane rating) is changed into high-octane rating product liquid to produce.
" white gasoline " refers to the volatile compounds of liquid hydrocarbon, and it usually containing a small amount of additive, is suitable as the fuel of spark-ignited internal combustion engine, does not carry out processing (see ASTM D4814) with lead compound.
The present invention relates to the method reclaiming the finished product ethanol composition for the formation of Denatured alcohol fuel composition of being produced by method of hydrotreating, and relate to Denatured alcohol fuel composition.Method of hydrotreating comprises and in the presence of a catalyst acetic acid is carried out hydrogenation.This hydrogenation process produces the crude ethanol product being different from the coarse ethanol composition that other ethanol production process produces.Such as, the coarse ethanol composition that fermenting process produces has low ethanol content.The coarse ethanol composition produced by petrochemical materials comprises other alcohol, particularly methyl alcohol, n-propyl alcohol and higher alcohol.Preferably the crude ethanol product that acetic acid hydrogenation produces is carried out being separated remove impurity and reclaim finished product ethanol composition.
Ethanol composition of the present invention, in one embodiment, comprises the ethanol of major portion and the Virahol of secondary part.Ethanol composition is ethanol mainly, containing 92wt.%-96wt.%, and such as 93wt.%-96wt.% or 95wt.%-96wt.% ethanol.Preferably, ethanol composition contains at least 92wt.% such as at least 93wt.% or at least 95wt.% ethanol.Higher amount of alcohol can be obtained, such as dehydrated alcohol by the water removing ethanol composition further.Virahol can by 95wppm-1,000wppm, and the amount of such as 110wppm-800wppm or 110wppm-400wppm exists.With regard to lower limit, in one embodiment, ethanol composition comprises at least 95wppm, such as at least 110wppm or at least 150wppm Virahol.With regard to the upper limit, in one embodiment, ethanol composition comprises and is less than 1,000wppm, such as, be less than 800wppm or be less than 400wppm Virahol.On the contrary, figure 3 shows the Virahol level of 176 conventional ethanol compositions.These ethanol composition derive from various usual sources and technology such as sugarcane is fermented, molasses fermented and Fiscber-Tropscb synthesis.As shown in Figure 3, each in these conventional ethanol compositions has very low isopropyl alcohol concentration, and neither one comprises the Virahol of the amount being greater than 94wppm.
In one embodiment, ethanol composition also comprises water, such as, be less than 8wt.%, be less than 5wt.% or be less than the water of amount of 2wt.%.In another embodiment, in ethanol composition, the weight ratio of Virahol and water is 1:80-1:800, such as 1:100-1:500.In one embodiment, ethanol composition does not comprise other compound that can detect substantially, and such as methyl alcohol, benzene and/or higher alcohol are as C 4+alcohol.In some embodiments, ethanol composition can comprise other impurity of minor amount, such as, in following table 7 describe those.
In another embodiment, the present invention relates to the ethanol composition comprising ethanol and at least two kinds of other alcohol.Described at least two kinds of other alcohol can be selected from n-propyl alcohol, Virahol, butanols, 2-butanols and isopropylcarbinol.Preferably, the one in described at least two kinds of other alcohol is Virahol.In these embodiments, Virahol is with at least 95wppm, and such as at least the amount of 110wppm or at least 150wppm exists.In preferred embodiments, when the weight percentage of described at least two kinds of other alcohol is added together, these at least two kinds other alcohol exist with the amount being less than 1wt.% altogether.
Although not bound by theory, think and form Virahol during acetic acid hydrogenation.Such as, Virahol can be formed by acetone hydrogenation.Acetone can be produced by the reaction of acetic acid ketonize.If n-propyl alcohol is present in ethanol composition, be then considered to be formed by the impurity in acetic acid feed.Ethanol composition of the present invention preferably comprises and is less than 0.5wt.%, such as, be less than 0.1wt.% or be less than the n-propyl alcohol of amount of 0.05wt.% n-propyl alcohol.Optionally, ethanol composition of the present invention preferably can have the n-propyl alcohol fewer than Virahol.The Virahol that the original position that the ethanol composition formed by the inventive method comprises higher amount than conventional ethanol composition is formed.Preferably, in ethanol composition of the present invention, n-propyl alcohol amount can be less than the amount of Virahol, such as less than Virahol amount 10% or less than Virahol amount by 50%.In addition, in one embodiment, in ethanol composition of the present invention, the weight ratio of Virahol and n-propyl alcohol can be 0.1:1-10:1, such as 0.5:1-10:1,1:1-5:1 or 1:1-2:1.With regard to the limit, the weight ratio of Virahol and n-propyl alcohol can be at least 0.5:1, such as at least 1:1, at least 1.5:1, at least 2:1, at least 5:1 or at least 10:1.In conventional ethanol production method, Virahol does not typically exist with above-mentioned amount.Therefore, the weight ratio of Virahol or n-propyl alcohol is conducive to more n-propyl alcohol, such as, be greater than 10:1.
In one embodiment of the invention, preferably Virahol is not joined in finished product ethanol composition at separation of ethanol with after reclaiming.The Virahol formed during acetic acid hydrogenation can in sepn process with ethanol by carrier band.
In addition, conventional hydro reaction often forms the acetaldehyde of a large amount compared with Virahol.Ethanol composition of the present invention comprises the acetaldehyde of low amounts, and other acetal compound.Preferably, in ethanol composition of the present invention, the amount of acetaldehyde is less than the amount of Virahol.Such as, the amount of acetaldehyde can be less than 50% of Virahol amount, such as, be less than 10% of Virahol amount or be less than 5% of Virahol amount.In ethanol composition of the present invention, the further weight ratio of Virahol and acetaldehyde can be 1:100-1:1000, such as 1:100-1:500.
In one embodiment, ethanol composition of the present invention comprises the organic impurity of minor amount.These organic impuritys can comprise acetaldehyde, acetic acid, diethyl acetal, ethyl acetate, n-propyl alcohol, methyl alcohol, butanols, 2-butanols, isopropylcarbinol, primary isoamyl alcohol, amylalcohol, benzene and/or their mixture.Advantageously, in one embodiment, ethanol composition comprises and is less than 1wt.%, such as, be less than 0.75wt.% or be less than the organic impurity of 0.5wt.%.Depend on the amount of these organic impuritys, impurity may have deleterious effect to ethanol composition.Such as, other alcohol in coarse ethanol composition can form other ester with acetic acid generation esterification.In addition, find that isopropylcarbinol, primary isoamyl alcohol and 2-methyl-1-butene alcohol (" active amyl alcohol ") impel the residual smell produced in ethanol and ethyl acetate combination thing.
In preferred embodiments, ethanol composition is substantially free of methyl alcohol and can comprises and is less than 10wppm, such as, be less than 1wppm methyl alcohol.In addition, in preferred embodiments, ethanol composition is substantially free of C 5alcohol and can comprise and be less than 10wppm, such as, be less than the C of 1wppm 5alcohol.
Known benzene, diox and prussiate show toxicity problem in ethanol composition.Typically, prussiate produces the fermentation process from using cassava as raw material.Ethanol composition of the present invention comprises these components of low amounts.Preferably, this ethanol composition contains benzene, diox and the prussiate of the amount that can't detect.
Hydrogenation technique
Now turning to the production of coarse ethanol composition, usually, forming second alcohol and water as reacted shown acetic acid hydrogenation below:
As described in the following table 1 and, dewater and ethanol outside, other compound can also be formed during acetic acid hydrogenation.
Suitable hydrogenation catalyst comprises and optionally comprises the first metal on a catalyst support and one or more the catalyzer optionally comprised in the second metal, the 3rd metal or other metal.First with optional second and the 3rd metal can be selected from: IB, Π Β, IIIB, IVB, VB, VIB, VIIB, VIII transition metal, lanthanide series metal, actinide metals or be selected from the metal of any race in IIIA, IVA, VA and VIA race.Preferable alloy combination with regard to some exemplary catalyst compositions comprises platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium and ruthenium/iron.Exemplary catalyzer is also described in U.S. Patent No. 7,608,744 and the U.S. announce in No.2010/0029995, by reference their are incorporated to herein in full.Other catalyzer is described in the U. S. application No.12/698 that the exercise question submitted on February 2nd, 2010 is " C atalysts for Making Ethanol from Acetic Acid ", in 968, it is incorporated in full herein by reference.
In an exemplary embodiment, this catalyzer comprises the first metal being selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.Preferably, the first metal is selected from platinum, palladium, cobalt, nickel and ruthenium.More preferably, the first metal is selected from platinum and palladium.When the first metal comprises platinum, due to the high demand to platinum, catalyzer preferably comprises the platinum of amount being less than 5wt.% and being such as less than 3wt.% or being less than 1wt.%.
As indicated above, this catalyzer optionally also comprises the second metal, and this second metal can play promotor usually.If existed, the second metal is preferably selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.More preferably, the second metal is selected from copper, tin, cobalt, rhenium and nickel.More preferably, the second metal is selected from tin and rhenium.
If catalyzer comprises two or more metals, such as the first metal and the second metal, then the first metal is optionally with 0.1-10wt.%, and the amount of such as 0.1-5wt.% or 0.1-3wt.% is present in catalyzer.Second metal is preferably with 0.1-20wt.%, and the amount of such as 0.1-10wt.% or 0.1-5wt.% exists.For the catalyzer comprising two or more metals, two or more metals described can alloying or can comprise no-alloyed metal solid solution or mixture each other.
Preferred metal ratio can depend on metal used in catalyzer and change.In some example embodiments, the first metal and bimetallic mol ratio are preferably 10:1-1:10, such as 4:1-1:4,2:1-1:2,1.5:1-1:1.5 or 1.1:1-1:1.1.
This catalyzer can also comprise the 3rd metal, and the 3rd metal is selected from above about any metal listed by the first or second metal, as long as the 3rd metal is different from the first and second metals.In preferred, the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.More preferably, the 3rd metal is selected from cobalt, palladium and ruthenium.When it is present, the gross weight of the 3rd metal is preferably 0.05-4wt.%, such as 0.1-3wt.% or 0.1-2wt.%.
Except one or more metals, exemplary catalyst also comprises carrier or modified support, and modified support refers to the carrier comprising solid support material and support modification agent, and described support modification agent regulates the acidity of solid support material.The gross weight of carrier or modified support is preferably 75wt.%-99.9wt.% based on this overall catalyst weight gauge, such as 78wt.%-97wt.% or 80wt.%-95wt.%.In the preferred embodiment using modified support, support modification agent is with based on overall catalyst weight gauge 0.1wt.%-50wt.%, and the amount of such as 0.2wt.%-25wt.%, 0.5wt.%-15wt.% or 1wt.%-8wt.% exists.
Suitable solid support material can comprise such as stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises siliceous supports, and such as silicon-dioxide, silica/alumina and IIA race silicate are as calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.Other carrier can include but not limited to ferriferous oxide (iron oxide), aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, carbon, graphite, high surface area graphite carbon, gac and their mixture.
In the production of ethanol, support of the catalyst can carry out modification with support modification agent.Preferably, support modification agent is the basic modifier with low volatility or non-volatility.This kind of basic modifier such as can be selected from: (i) alkaline earth metal oxide, (ii) alkalimetal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) IIB family metal oxide, (vi) IIB race metal metasilicates, (vii) IIIB family metal oxide, (viii) IIIB race metal metasilicates and their mixture.Except oxide compound and metasilicate, the properties-correcting agent of other type comprising nitrate, nitrite, acetate and lactic acid salt can be used.Preferably, support modification agent is selected from oxide compound and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium and zinc, and aforesaid any mixture.Preferably, support modification agent is Calucium Silicate powder, and more preferably calcium metasilicate (CaSiO 3).If support modification agent comprises calcium metasilicate, then calcium metasilicate be at least partially preferably crystallized form.
Preferred silica support materials is SS61138 high surface area (HSA) silica catalyst supports from Saint-Gobain NorPro.Saint-Gobain NorProSS61138 silicon-dioxide is containing the high surface area silica of the 95wt.% that has an appointment; About 250m 2the surface-area of/g; The mean pore sizes of about 12nm; By the about 1.0cm that pressure mercury hole method of masurement is measured 3the average pore sizes of/g and about 0.352g/cm 3(22lb/ft 3) tap density.
Preferred silica/alumina solid support material is KA-160 (Sud Chemie) silica spheres, and it has the specific diameter of about 5mm, the density of about 0.562g/ml, about 0.583gH 2the specific absorption of O/g carrier, about 160-175m 2the surface-area of/g and the pore volume of about 0.68ml/g.
Under those of skill in the art would recognize that the processing condition that select to make catalyst body to tie up to for generating ethanol to solid support material, there is suitable activity, selectivity and robustness (robust).
The metal of catalyzer can disperse throughout whole carrier, applies (eggshell) or modification (decorate) on the outer surface of the support on carrier surface.
Be applicable to catalyst composition of the present invention formed, although the such as chemical vapour deposition of other method can also be used preferably by the metal impregnation of modified support.Such dipping technique is described in U.S. Patent No. 7,608,744 mentioned above, the U.S. announces No.2010/0029995 and U. S. application No.12/698, in 968, they is incorporated in full herein by reference.
As the skilled person will be readily appreciated, some embodiments according to one embodiment of the invention, acetic acid hydrogenation being formed the method for ethanol can comprise the various structures using fixed-bed reactor or fluidized-bed reactor.In many embodiments of the present invention, " thermal insulation " reactor can be used; That is, have and seldom or not need the internal pipeline system (plumbing) through reaction zone add or remove heat.In other embodiments, radial flow reactor or multiple reactor can be used, or the serial reaction device that there is or do not have heat exchange, cooling or introduce other charging can be used.Or, the shell-tube type reactor being equipped with heat transmission medium can be used.In many cases, reaction zone can be contained in single container or between have in the series containers of interchanger.
In preferred embodiments, catalyzer uses in the fixed-bed reactor of such as pipeline or catheter shape, the reactant typically wherein being vaporous form through or by described catalyzer.Other reactor can be used, such as fluidized-bed or ebullated bed reactor.In some cases, hydrogenation catalyst can be combined with inert material to regulate reaction mass to flow through the pressure drop of catalyst bed and the duration of contact of reactant compound and granules of catalyst.
Hydrogenation reaction can be carried out in liquid phase or gas phase.Preferably, under following condition, this reaction is carried out in the gas phase.Temperature of reaction can be 125 DEG C-350 DEG C, such as 200 DEG C-325 DEG C, 225 DEG C-300 DEG C or 250 DEG C-300 DEG C.Pressure can be 10KPa-3000KPa (about 1.5-435psi), such as 50KPa-2300KPa or 100KPa-1500KPa.Can by reactant to be greater than 500hr -1, such as, be greater than 1000hr -1, be greater than 2500hr -1or be even greater than 5000hr -1gas hourly space velocity (GHSV) to entering reactor.With regard to scope, GHSV can be 50hr -1-50,000hr -1, such as 500hr -1-30,000hr -1, 1000hr -1-10,000hr -1or 1000hr -1-6500hr -1.
Optionally under being just enough to overcome the pressure through the pressure drop of catalytic bed, carry out hydrogenation with selected GHSV, although do not limit the higher pressure of use, should be understood that at high air speed such as 5000hr -1or 6,500hr -1the lower sizable pressure drop may experienced by reactor beds.
Although the every mole of acetic acid of this reaction consumes 2 mol of hydrogen thus produce 1 moles ethanol, in incoming flow, the actual mol ratio of hydrogen and acetic acid can be about 100:1-1:100, such as 50:1-1:50,20:1-1:2 or 12:1-1:1.Most preferably, the mol ratio of hydrogen and acetic acid is greater than 2:1, such as, be greater than 4:1 or be greater than 8:1.
Contact or the residence time also can vary widely, and these depend on the variable as the amount of acetic acid, catalyzer, reactor, temperature and pressure.When using catalyst system except fixed bed, typical duration of contact, at least for gas-phase reaction, preferred duration of contact was 0.1-100 second for part second is to being greater than some hours, such as 0.3-80 second or 0.4-30 second.
The raw material, acetic acid and the hydrogen that use about the inventive method derived from any suitable source, can comprise Sweet natural gas, oil, coal, biomass etc.As an example, carbonylation of methanol, oxidation of acetaldehyde, oxidation of ethylene, oxidative fermentation and production of acetic acid by anaerobic fermentation can be passed through.Due to oil and natural gas price volalility, more or less become expensive, so cause concern gradually by alternative carbon source production acetic acid and the method for intermediate e as methyl alcohol and carbon monoxide.Especially, when oil and gas is compared relatively costly, produce acetic acid by the synthesis gas (" synthetic gas ") derived from any available carbon source and may become favourable.Such as, its disclosure is incorporated to herein by U.S. Patent No. 6,232,352(by reference) teach transformation methanol device in order to manufacture the method for acetic acid.By transformation methanol device, for new acetic acid device, produce relevant substantial contribution expense with CO and be significantly reduced or eliminate to a great extent.Make all or part synthetic gas turn to from methanol-fueled CLC loop and be supplied to separator unit to reclaim CO and hydrogen, then by them for the production of acetic acid.In addition to acetic acid, this method can also for the preparation of the available hydrogen of relevant the present invention.
The methanol carbonylation process being suitable for acetic acid production is described in U.S. Patent No. 7,208, and 624,7,115,772,7,005,541,6,657,078,6,627,770,6,143,930,5,599,976,5,144,068,5,026,908,5,001,259 and 4,994, in 608, by reference their disclosure is incorporated to herein.Optionally, alcohol production and this methanol carbonylation process can be integrated.
U.S. Patent No. RE 35,377(is also incorporated to herein by reference) provide a kind of by making the method for carbonaceous material such as oil, coal, Sweet natural gas and conversion of biomass material methanol.The method comprises makes solid and/or the hydrogasification of liquid carbon-containing material to obtain process gas, with other Sweet natural gas by this process gas steam pyrolysis to form synthetic gas.Be can turn to the methyl alcohol of acetic acid by carbonyl by this Synthetic holography.The method produces equally as the above-mentioned relevant spendable hydrogen of the present invention.U.S. Patent No. 5,821,111 and U.S. Patent No. 6,685,754 disclose and a kind of useless biomass be converted into the method for synthetic gas by gasification, by reference their disclosure is incorporated to herein.
In an optional embodiment, other carboxylic acid and acid anhydrides can also be comprised to the acetic acid entering hydrogenation reaction, and acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises the compound that one or more are selected from acetic acid, diacetyl oxide, acetaldehyde and their mixture.In the method for the invention can also by these other compound hydrogenation.In some embodiments, in propyl alcohol is produced, the existence of carboxylic acid such as propionic acid or its acid anhydrides can be useful.
As an alternative, can directly by reference it be incorporated in full herein from U.S. Patent No. 6,657,078() described in the flasher of a class methanol carbonylation unit take out the acetic acid of vaporous form as crude product.Such as, thick vapor product can not needed condense acetic acid and lighting end directly to entering ethanol building-up reactions district of the present invention or except anhydrating, thus save overall craft expense.
Acetic acid can be made to gasify at the reaction temperatures, then the acetic acid of gasification can be fed together in company with undiluted state or with the hydrogen that carrier gas such as nitrogen, argon gas, helium, the carbonic acid gas etc. of relative inertness dilute.For making reaction run in the gas phase, the temperature in Controlling System is answered to make it not drop to dew point lower than acetic acid.In one embodiment, acetic acid can be made at a particular pressure in the gasification of acetic acid boiling point, then the acetic acid of gasification can be heated to reactor inlet temperature further.In another embodiment, be passed in lower than the acetic acid at the temperature of acetic acid boiling point by making hydrogen, circulation gas, another kind of suitable gas or their mixture and make acetic acid change vapor state into, thus soak carrier gas by acetic acid vapor, then the steam of mixing is heated to reactor inlet temperature always.Preferably, by making hydrogen and/or circulation gas through being in or making acetic acid change steam into lower than the acetic acid at the temperature of 125 DEG C, then the gaseous stream of merging is heated to reactor inlet temperature.
Especially, the hydrogenation of acetic acid can obtain acetic acid advantageous conversion rate and to the favourable selectivity of ethanol and productive rate.For the present invention, term " transformation efficiency " refers in charging the amount of the acetic acid of the compound be converted in addition to acetic acid.Transformation efficiency represents by based on the molecular fraction of acetic acid in charging.Described transformation efficiency can be at least 10%, such as at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.Although expect the catalyzer with high conversion such as at least 80% or at least 90%, when the selectivity height of ethanol, low transformation efficiency also can accept in some embodiments.Certainly, should fully understand, in many cases, make up transformation efficiency by suitable recycle stream or the larger reactor of use, but be comparatively difficult to make up poor selectivity.
Selectivity represents by the molecular fraction based on the acetic acid transformed.The often kind of compound transformed by acetic acid should be understood there is independently selectivity and this selectivity does not rely on transformation efficiency.Such as, if 50 of the acetic acid transformed % by mole are converted into ethanol, then ethanol selectivity is 50%.Preferably, catalyzer is at least 60% to the selectivity of ethoxylate, such as at least 70% or at least 80%.As used herein, term " ethoxylate " specifically refers to compound ethanol, acetaldehyde and ethyl acetate.Preferably, the selectivity of ethanol is at least 80%, such as at least 85% or at least 88%.The preferred embodiment of this hydrogenation process also has the low selectivity to less desirable product such as methane, ethane and carbonic acid gas.Preferably 4% is less than to the selectivity of these less desirable products, such as, is less than 2% or be less than 1%.More preferably, these less desirable products can't detect.The formation of alkane can be low, and ideally, the acetic acid through catalyzer is less than 2%, be less than 1% or be less than 0.5% and be converted into alkane, and described alkane has very little value in addition to being a fuel.
Based on the grams of kilogram regulation product such as ethanol that meter is per hour formed of used catalyst during " productive rate " refers to hydrogenation as used herein, the term.Preferred productive rate is every kg catalyst at least 200 grams of ethanol per hour, and such as every kg catalyst at least 400 grams of ethanol per hour are or every kg catalyst at least 600 grams of ethanol per hour.With regard to scope, described productive rate is preferably every kg catalyst 200-3 per hour, 000 gram of ethanol, such as 400-2, and the per hour or 600-2 of 500 grams of every kg catalyst of ethanol, 000 gram of every kg catalyst of ethanol is per hour.
In various embodiments, the crude ethanol product produced by method of hydrotreating, before any processing example is subsequently as purification and separation, typically will comprise unreacted acetic acid, second alcohol and water.As used herein, term " crude ethanol product " refers to any composition comprising 5-70wt.% ethanol and 5-35wt.% water.In some example embodiments, crude ethanol product comprises based on this crude ethanol product total weight 5wt.%-70wt.%, the ethanol of the amount of such as 10wt.%-60wt.% or 15wt.%-50wt.%.Preferably, crude ethanol product contains at least 10wt.% ethanol, at least 15wt.% ethanol or at least 20wt.% ethanol.
Depend on transformation efficiency, crude ethanol product typically also will comprise unreacted acetic acid, such as, be less than 90wt.%, such as, be less than 80wt.% or be less than the amount of 70wt.%.With regard to scope, unreacted acetic acid is preferably 0-90wt.%, such as 5-80wt.%, 15-70wt.%, 20-70wt.% or 25-65wt.%.Because form water in reaction process, water will usually such as with 5-35wt.%, and the amount as 10-30wt.% or 10-26wt.% is present in crude ethanol product.During acetic acid hydrogenation or by side reaction, also can produce ethyl acetate, and it can such as with 0-20wt.%, the amount as 0-15wt.%, 1-12wt.% or 3-10wt.% exists.Also can produce acetaldehyde by side reaction and it can such as with 0-10wt.%, the amount as 0-3wt.%, 0.1-3wt.% or 0.2-2wt.% exists.
Other component is ester, ether, aldehyde, ketone, alkane and carbonic acid gas such as, if can detect, can altogether to be less than 10wt.%, and the amount being such as less than 6wt.% or being less than 4wt.% exists.With regard to scope, other component can by 0.1-10wt.%, and the amount of such as 0.1-6wt.% or 0.1-4wt.% exists.The exemplary of coarse ethanol compositing range is provided in table 1.
Purifying
Figure 1 shows and be suitable for acetic acid hydrogenation and the hydrogenation system 100 from crude product mixture separating alcohol according to one embodiment of the invention.System 100 comprises reaction zone 101 and distillation zone 102.Reaction zone 101 comprises reactor 103, hydrogen feed line 104 and acetic acid feed pipeline 105.Distillation zone 102 comprises flasher 106, first tower 107, second tower 108, the 3rd tower 109 and the 4th tower 123.Respectively by pipeline 104 and 105 by hydrogen and acetic acid to entering vaporizer 110 to produce vapor feed stream in the pipeline 111 being directed to reactor 103.In one embodiment, pipeline 104 and 105 can be merged and such as with a kind of stream simultaneously containing hydrogen and acetic acid jointly to entering vaporizer 110.In pipeline 111, the temperature of vapor feed stream is preferably 100 DEG C-350 DEG C, such as 120 DEG C-310 DEG C or 150 DEG C-300 DEG C.As shown in Figure 1, any charging of not gasification is shifted out from vaporizer 110, and can be recycled to wherein.In addition, although figure 1 shows the top of pipeline 111 directed response device 103, pipeline 111 can the sidepiece of directed response device 103, top or bottom.Other amendment and other integral part of reaction zone 101 is described below in accompanying drawing 2.
Reactor 103 contains for making carboxylic acid, the catalyzer of preferred acetic acid hydrogenation.In one embodiment, one or more protection bed (not shown) guard catalyst can be used to avoid suffering charging or return/recycle stream in contained toxic substance or less desirable impurity.This kind of protection bed can use in vapor stream or liquid stream.Suitable protection bed material is known in the art and comprises such as carbon, silicon-dioxide, aluminum oxide, pottery or resin.On the one hand, make protection bed medium functionalized to trap particular matter such as sulphur or halogen.During hydrogenation process, by pipeline 112, coarse ethanol product is preferably taken out from reactor 103 continuously.The condensation of coarse ethanol product, to entering flasher 106, can be this in turn provides steam stream and liquid stream.In one embodiment, flasher 106, preferably at 50 DEG C-500 DEG C, such as, operates at the temperature of 70 DEG C-400 DEG C or 100 DEG C-350 DEG C.In one embodiment, the pressure of flasher 106 is preferably 50KPa-2000KPa, such as 75KPa-1500KPa or 100-1000KPa.In a preferred embodiment, the temperature and pressure of flasher is similar to the temperature and pressure of reactor 103.
The vapor stream leaving flasher 106 can comprise hydrogen and hydrocarbon, can be carried out cleaning and/or turning back to reaction zone 101 by pipeline 113.As shown in Figure 1, the returning part of vapor stream passes compressor 114 and merges with hydrogen feed, jointly to entering vaporizer 110.
Using from flasher 106 liquid take out and be pumped into the first tower 107(also referred to as acid separation column as feed composition by pipeline 115) sidepiece.The content of pipeline 115 typically will be substantially similar to the product directly obtained from reactor, and in fact can also be called crude ethanol product.But the feed composition in pipeline 115 is preferably substantially free of hydrogen, carbonic acid gas, methane or ethane, they are moved out of by flasher 106.The exemplary compositions of liquid in pipeline 115 is provided in table 2.It should be understood that liquid line 115 can containing the component in other component (unlisted) such as charging.
In the table of whole the application, be less than (<) and if shown in amount be preferably do not exist then to exist by trace or with the amount being greater than 0.0001wt.%.
" other ester " in table 2 can include but not limited to ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate or their mixture." other ether " in table 2 can include but not limited to diethyl ether, methyl ethyl ether, isobutyl ethyl ether or their mixture." other alcohol " in table 2 can include but not limited to methyl alcohol, Virahol, n-propyl alcohol, propyl carbinol or their mixture.In one embodiment, feed composition such as pipeline 115 can comprise with the propyl alcohol of the amount of 0.001-0.1wt.%, 0.001-0.05wt.% or 0.001-0.03wt.% as Virahol and/or n-propyl alcohol.Should be understood that these other components can carrier band in any distillate flow described herein or residual stream, and unless otherwise indicated, will not to be further described herein.
When in pipeline 115, the content of acetic acid is less than 5wt.%, acid separation column 107 can be skipped and pipeline 115 can be introduced directly into the second tower 108(be also called light fraction tower herein).
In embodiment in fig. 1, pipeline 115 is introduced the bottom of the first tower 107, such as Lower Half or lower 1/3rd.In the first tower 107, unreacted acetic acid, part water and other heavy component (if existence) are shifted out from the composition pipeline 115 and preferably take out as resistates continuously.Some or all resistatess can be made to be returned by pipeline 116 and/or reaction zone 101 is got back in recirculation.First tower 107 also forms overhead product, is taken out by this overhead product in pipeline 117, and can by it such as with 10:1-1:10, and the ratio as 3:1-1:3 or 1:2-2:1 carries out condensation and backflow.
Any one in tower 107,108,109 or 123 can comprise can carry out being separated and/or any distillation tower of purifying.Described tower preferably comprises and has 1-150 column plate, the such as tray column of 10-100 column plate, a 20-95 column plate or 30-75 column plate.Column plate can be sieve plate, fixed float valve plate, mobile valve tray or other suitable design any known in the art.In other embodiments, packing tower can be used.For packing tower, structured packing or random packing can be used.Described tower or filler can be configured by a kind of continuous tower or they can be configured by two or more towers makes the steam from first paragraph enter second segment and make the liquid from second segment enter first paragraph simultaneously, etc.
The associated condenser that can use together with each distillation tower and liquid separation container can have any conventional design and be simplified in fig. 1.As shown in Figure 1, heat supply can be supplied to recycle column bottoms stream to the bottom of each tower or by interchanger or reboiler.In some embodiments, the reboiler of other type can also be used, such as internal reboiler.Any heat produced during the heat being supplied to reboiler can be obtained from the process integrated with described reboiler or be obtained from that external source is such as another kind of produces hot chemical process or boiler.Although show a reactor and a flasher in fig. 1, additional reactor, flasher, condenser, heating unit and other parts can be used in embodiments of the invention.As those skilled in the art can recognize, the various condensers, pump, compressor, reboiler, rotary drum, valve, junctor, separation vessel etc. that are generally used for carrying out chemical process can also be carried out combining and are used in method of the present invention.
Temperature and pressure used in any tower can change.As practical situation, usually can use the pressure of 10KPa-3000KPa in that region, although subatmospheric pressure and superatmospheric pressure can be used in some embodiments.Temperature in regional is using in the scope between the boiling point of the usual composition being removed as overhead product and the boiling point of composition be removed as resistates.Those skilled in the art will recognize that, in the distillation tower of operation, the temperature of given position depends on material composition in this position and the pressure of tower.In addition, feeding rate can depend on production technique scale and change, if be described, then can generally refer to according to feed weight ratio.
When tower 107 operates at normal atmospheric pressure, the temperature of the resistates left from tower 107 in pipeline 116 is preferably 95 DEG C-120 DEG C, such as 105 DEG C-117 DEG C or 110 DEG C-115 DEG C.The temperature of the overhead product left from tower 107 in pipeline 117 is preferably 70 DEG C-110 DEG C, such as 75 DEG C-95 DEG C or 80 DEG C-90 DEG C.In other embodiments, the pressure of the first tower 107 can be 0.1KPa-510KPa, such as 1KPa-475KPa or 1KPa-375KPa.The overhead product of the first tower 107 and the exemplary compositions of resistates composition is provided in following table 3.Should also be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.Conveniently, the overhead product of the first tower and resistates may also be referred to as " the first overhead product " or " the first resistates ".The overhead product of other tower or resistates also can be mentioned they to be distinguished from each other out with similar digital modifier (second, third etc.), but this kind of modifier should not be interpreted as requiring any special separation sequence.
As shown in table 3, although not bound by theory, unexpected and unexpectedly find, when detecting the acetal of any amount in the charging being incorporated into acid separation column (the first tower 107), acetal seems to decompose in this tower to make to exist less in overhead product and/or resistates or even do not have detectable amount.
Depend on reaction conditions, the crude ethanol product leaving reactor 103 in pipeline 112 can comprise ethanol, acetic acid (unconverted), ethyl acetate and water.After leaving reactor 103, between the component that crude ethanol product is wherein comprised before joining flasher 106 and/or the first tower 107, non-catalytic balanced reaction can be there is.As shown below, this balanced reaction trends towards driving crude ethanol product to reach balance between ethanol/acetic acid and ethyl acetate/water.
Before guiding distillation zone 102, in the situation of temporary storage in such as storage tank, the residence time of prolongation can be met with at crude ethanol product.Usually, the residence time between reaction zone 101 and distillation zone 102 is longer, and ethyl acetate is formed more.Such as, when the residence time between reaction zone 101 and distillation zone 102 is greater than 5 days, significantly more ethyl acetate may be formed with the loss of ethanol.Therefore, shorter between usual preferred reaction district 101 and distillation zone 102 residence time maximizes to make the amount of the ethanol of formation.In one embodiment, storage tank (not shown) is included between reaction zone 101 and distillation zone 102 and continues to many 5 days for interim storage from the liquid ingredient of pipeline 115, such as at the most 1 day or 1 hour at the most.In preferred embodiments, tank is not comprised and by the liquid of condensation directly to entering the first distillation tower 107.In addition, the speed that uncatalyzed reaction occurs can improve along with the temperature of the crude ethanol product such as in pipeline 115 and improve.More than 30 DEG C, at such as, temperature more than 40 DEG C or more than 50 DEG C, these speed of reaction can have problems especially.Therefore, in one embodiment, to make in pipeline 115 or liquid ingredient temperature in optional storage tank maintains to be in and is less than 40 DEG C, such as, be less than 30 DEG C or be less than the temperature of 20 DEG C.One or more refrigerating unit can be used to reduce the temperature of liquid in pipeline 115.
As discussed above, storage tank (not shown) can be included between reaction zone 101 and distillation zone 102 for optional at the temperature of about 21 DEG C interim storage from the liquid ingredient such as 1-24 hour of pipeline 115, and correspond respectively to and form the ethyl acetate of 0.01wt.%-1.0wt.%.In addition, the speed that uncatalyzed reaction occurs can improve along with the temperature of crude ethanol product and improve.Such as, along with the crude ethanol product temperature in pipeline 115 brings up to 21 DEG C from 4 DEG C, formed ethyl acetate speed can from about 0.01wt.%/hour to bring up to about 0.005wt.%/hour.Therefore, in one embodiment, to make in pipeline 115 or liquid ingredient temperature in optional storage tank maintains to be in and is less than 21 DEG C, such as, be less than 4 DEG C or be less than the temperature of-10 DEG C.
In addition, have now found that, above-mentioned balanced reaction can also be conducive to forming ethanol in the top area of the first tower 107.
As shown in Figure 1, optionally the overhead product of tower 107 such as top stream is carried out condensation and the preferred reflux ratio with 1:5-10:1 refluxes.Overhead product in pipeline 117 preferably comprises ethanol, ethyl acetate and water and other impurity, its formation due to binary and ternary azeotrope and may be difficult to be separated.
The first overhead product in pipeline 117 is incorporated into the second tower 108(also referred to as " light fraction tower "), preferably introduce at the middle portion such as middle 1/2nd or middle 1/3rd of tower 108.As an example, when not have to use the tower of 25 column plates in the tower of water extracting, pipeline 117 is introduced at column plate 17 place.In one embodiment, the second tower 108 can be extractive distillation tower.In such an implementation, extraction agent such as water can be joined the second tower 108.If extraction agent comprises water, then its can obtain from external source or return from the inside from other tower one or more/recirculation line obtains.
Second tower 108 can be tray column or packing tower.In one embodiment, the second tower 108 has 5-70 column plate, such as the tray column of 15-50 column plate or 20-45 column plate.
Although the temperature and pressure of the second tower 108 can change, the temperature of second resistates that ought under atmospheric pressure leave from the second tower 108 in pipeline 118 is preferably 60 DEG C-90 DEG C, such as 70 DEG C-90 DEG C or 80 DEG C-90 DEG C.The temperature of the second overhead product left from the second tower 108 in pipeline 120 is preferably 50 DEG C-90 DEG C, such as 60 DEG C-80 DEG C or 60 DEG C-70 DEG C.Tower 108 can under atmospheric pressure operate.In other embodiments, the pressure of the second tower 108 can be 0.1kPa-510kPa, such as 1kPa-475kPa or 1kPa-375kPa.The overhead product of the second tower 108 and the exemplary compositions of resistates composition is provided in following table 4.It should be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.
The weight ratio of the ethanol in the ethanol in the second resistates and the second overhead product is preferably at least 3:1, such as at least 6:1, at least 8:1, at least 10:1 or at least 15:1.The weight ratio of the ethyl acetate in the ethyl acetate in the second resistates and the second overhead product is preferably less than 0.4:1, such as, be less than 0.2:1 or be less than 0.1:1.Using water as in the embodiment of the extraction column into extraction agent as the second tower 108, the weight ratio of the ethyl acetate in the ethyl acetate in the second resistates and the second overhead product is close to zero.
As shown, by from the second resistates (it comprises second alcohol and water) bottom the second tower 108 by pipeline 118 to entering the 3rd tower 109(also referred to as " product tower ").More preferably, the second resistates in pipeline 118 is introduced the bottom of the 3rd tower 109, such as Lower Half or lower 1/3rd.3rd tower 109 reclaims ethanol (being preferably pure substantially except azeotropic water-content) with the overhead product in pipeline 119.The overhead product of the 3rd tower 109 is preferably pressed shown in accompanying drawing 1, such as, reflux with the reflux ratio of 1:10-10:1 as 1:3-3:1 or 1:2-2:1.The 3rd resistates (preferably mainly comprising water) in pipeline 121 preferably shifts out from system 100 or partly can turn back to any part of system 100.3rd tower 109 is preferably tray column as above and preferably under atmospheric pressure operates.The temperature of the 3rd overhead product left from the 3rd tower 109 in pipeline 119 is preferably 60 DEG C-110 DEG C, such as 70 DEG C-100 DEG C or 75 DEG C-95 DEG C.When this tower under atmospheric pressure operates, the temperature leaving the 3rd resistates of the 3rd tower 109 is preferably 70 DEG C-115 DEG C, such as 80 DEG C-110 DEG C or 85 DEG C-105 DEG C.The overhead product of the 3rd tower 109 and the exemplary compositions of resistates composition is provided in following table 5.It should be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.
Ethanol composition can comprise impurity mentioned above.In some embodiments, ethanol composition can also comprise other compound producing autoreaction process or sepn process.Can usually can by being retained on a small quantity the 3rd overhead product from these compounds of charging or crude reaction product carrier band in still-process.Such as, other compound described can be less than 0.1wt.% by the total weight based on the 3rd overhead product composition, and the amount being such as less than 0.05wt.% or being less than 0.02wt.% is present in.In one embodiment, one or more side line stream can remove impurity from any one tower 107,108 and/or 109 in system 100.At least one side line stream of preferred use removes impurity from the 3rd tower 109.Impurity can be carried out cleaning and/or being retained in system 100.
As hereafter described in more detail, can use one or more additional separation systems, such as distillation tower (as finishing column) or molecular sieve are further purified the 3rd overhead product in pipeline 119 to form dehydrated alcohol product flow, i.e. " finished product dehydrated alcohol ".
Turning back to the second tower 108, second overhead product preferably presses shown in accompanying drawing 1, and such as, with 1:10-10:1, the reflux ratio as 1:5-5:1 or 1:3-3:1 refluxes.Can by pipeline 120 by the second overhead product to the 4th tower 123 entered also referred to as " de-acetaldehyde tower ".In the 4th tower 123, the second overhead product is separated into and in pipeline 124, comprises the 4th overhead product of acetaldehyde and in pipeline 125, comprise the 4th residue of ethyl acetate.4th overhead product is preferably with 1:20-20:1, and the reflux ratio of such as 1:15-15:1 or 1:10-10:1 refluxes, and part the 4th overhead product turns back to reaction zone 101 as shown by pipeline 124.Such as, the 4th overhead product and acetic acid feed can be converged, join in vaporizer 110 or directly join in reactor 103.As shown, the acetic acid in the 4th overhead product and feeding line 105 is co-fed to vaporizer 110.Not bound by theory, because acetaldehyde can be added hydrogen evolution ethanol, the stream containing acetaldehyde is recycled to reaction zone and improves the yield of ethanol and reduce the generation of by product and refuse.In another embodiment (not shown), can when carrying out or not being further purified by acetaldehyde Collection and use in addition, to prepare the useful products including but not limited to propyl carbinol, 1,3 butylene glycol and/or crotonic aldehyde and derivative.
Can be cleaned by the 4th residue of pipeline 125 by the 4th tower 123.4th residual owner will comprise ethyl acetate and ethanol, and they can be suitable as solvent mixture or be used in ester production.In a preferred embodiment, shifted out by acetaldehyde from the second overhead product the 4th tower 123, making not exist in the residue of tower 123 can the acetaldehyde of detection limit.
4th tower 123 is preferably tray column as above and preferably higher than air pressing operation.In one embodiment, pressure is 120kPa-5000kPa, such as 200kPa-4,500kPa or 400kPa-3000kPa.In preferred embodiments, the 4th tower 123 can operate under the pressure higher than the pressure of other tower.
The temperature of the 4th overhead product left from the 4th tower 123 in pipeline 124 is preferably 60 DEG C-110 DEG C, such as 70 DEG C-100 DEG C or 75 DEG C-95 DEG C.The temperature of the resistates left from the 4th tower 125 is preferably 70 DEG C-115 DEG C, such as 80 DEG C-110 DEG C or 85 DEG C-110 DEG C.The overhead product of the 4th tower 123 and the exemplary compositions of resistates composition is provided in following table 6.It should be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.
Although show a reactor and a flasher in fig. 1, additional reactor and/or parts can be comprised in each optional embodiment of the present invention.Accompanying drawing 2 expression comprises double-reactor 103,103 ', two flasher 106,106 ', the hydrogenation system 100 ' of interchanger 130 and preheater 131.In this embodiment, in interchanger 130, the acetic acid in pipeline 105 heated with the recirculation acetic acid in pipeline 116 together with the recirculation acetaldehyde from pipeline 124 and deliver to vaporizer 110 by pipeline 132.The temperature of the content of pipeline 132 is preferably 30 DEG C-150 DEG C, such as 50 DEG C-130 DEG C or 75 DEG C-120 DEG C.By pipeline 104 by hydrogen to entering vaporizer 110, its formed evaporation stream 111.Evaporation stream 111 is through preheater 131, and stream 111 is heated to preferably 200 DEG C-300 DEG C by further, the temperature of such as 210 DEG C-275 DEG C or 220 DEG C-260 DEG C.Then by the stream of heating to entering the first reactor 103.In order to control exothermic heat of reaction, by pipeline 133 crude product mixture shifted out from the first reactor 103 and cooling to entering before the second reactor 103 ', making to maintain with the temperature of the reactant of catalyst exposure and product and to be in or minimum with the generation of the undesirably by product making to comprise methane, ethane, carbonic acid gas and/or carbon monoxide lower than 310 DEG C.In addition, higher than at about 320 DEG C, corrosion can become serious thus make to use the special and alloy material of costliness.Content in pipeline 133 temperature is after the cooling period preferably 200 DEG C-300 DEG C, such as 210 DEG C-275 DEG C or 220 DEG C-260 DEG C.Reactor 103 and 103 ' can have identical size and structure or they and can be of different sizes and construct.The catalyzer of each reactor preferably containing identical type, although can use other and/or different catalyzer for each reactor.As an example, above-mentioned catalyzer can be utilized.In addition, the mixture of catalyzer, catalyst mixture and inert material can be utilized and/or there is the catalyzer of different activities metal concentration.Such as, catalyzer can comprise the same item shaped metal of metal ratio variation.By pipeline 112, crude ethanol product is preferably taken out continuously from reactor 103 ', and be conveyed through interchanger 130 in condensation with before entering the first flasher 106 as heating medium.Therefore, the heat from crude ethanol product can be advantageously utilized acetic acid feed to be preheated before it introduces vaporizer 110.Conversely, acetic acid feed can be used to be cooled before it introduces the first flasher 106 by crude ethanol product as heat-eliminating medium.The vapor stream leaving the first flasher 106 comprises hydrogen and hydrocarbon, can be carried out cleaning and/or turning back to reaction zone 101 by pipeline 113.As shown in Figure 2, at least part of recirculation vapor stream is through compressor 114 and with hydrogen co-fed (or merge with hydrogen, then co-fed) to vaporizer 110.
By pipeline 134 by the remaining liq taking-up in flasher 106 and to entering the second flasher 106 ' to remove any residual vapor be dissolved in this liquid.Second flasher 106 ' can operate at the temperature lower than the first flasher 106 and/or pressure.In one embodiment, the temperature of the second flasher 106 ' is preferably 20 DEG C-100 DEG C, such as 30 DEG C-85 DEG C or 40 DEG C-70 DEG C.In one embodiment, the temperature of the second flasher 106 ' is preferably low at least 50 DEG C than the first flasher 106, such as low at least 75 DEG C or low at least 100 DEG C.The pressure of the second flasher 106 ' is preferably 0.1kPa-1000kPa, such as 0.1kPa-500kPa or 0.1kPa-100kPa.In one embodiment, the pressure of the second flasher 106 ' preferably than the low at least 50kPa of the first flasher 106, such as low at least 100kPa or low at least 200kPa.The vapor stream 135 leaving the second flasher can comprise hydrogen and hydrocarbon, it can be carried out cleaning and/or turning back to reaction zone according to the mode similar with the first flasher 106.As such as about as described in accompanying drawing 1, the remaining liq in flasher 106 ' is taken out and is pumped into the sidepiece of the first tower (not shown in accompanying drawing 2) by pipeline 115 and is further purified formation alcohol product stream i.e. " finished product ethanol ".
Finished product ethanol composition
The finished product ethanol composition obtained by the inventive method preferably comprises the Virahol of ethanol, water and minor amount.As indicated above, preferably, ethanol composition is ethanol mainly, containing 92wt.%-96wt.%, and such as 93wt.%-96wt.% or 95wt.%-96wt.% ethanol.In addition, in ethanol composition, the amount of Virahol is 95wppm-1,000wppm, such as 110wppm-800wppm or 110wppm-400wppm.
In another embodiment, ethanol composition comprises and is less than 270wppm, such as, be less than n-propyl alcohol altogether and the Virahol of 200wppm.With regard to scope, ethanol composition comprises 95wppm-270wppm, the n-propyl alcohol altogether of such as 100wppm-250wppm or 120wppm-200wppm and Virahol.In preferred embodiments, in ethanol composition, the total amount of Virahol and n-propyl alcohol is less than 1,000wppm, is usually such as less than 400wppm or is less than 200wppm.
In another embodiment, ethanol composition comprises the alcohol except ethanol and Virahol of ethanol, Virahol and low amounts, such as methyl alcohol, n-propyl alcohol and C 4+alcohol.In one embodiment, ethanol composition comprises and is less than 350wppm, such as, be less than 300wppm or be less than the alcohol except ethanol and Virahol of 275wppm.With regard to scope, said composition can comprise 1wppm-350wppm, the alcohol except ethanol and Virahol of the amount of such as 100wppm-325wppm.
In addition, ethanol composition can comprise a small amount of various organic impuritys.The example of these impurity comprises acetaldehyde, acetic acid, diethyl acetal, ethyl acetate, n-propyl alcohol, methyl alcohol, butanols, 2-butanols, isopropylcarbinol, primary isoamyl alcohol, amylalcohol, benzene and their mixture.In preferred embodiments, ethanol composition of the present invention comprises the organic impurity of low amounts, such as, be less than 1wt.%, be less than 0.75wt.% or be less than 0.5wt.% organic impurity.In another embodiment, ethanol composition of the present invention comprises the C of low amounts (if any) 5alcohol.Such as, ethanol composition can comprise and be less than 0.005wt.%, such as, be less than 0.001wt.% or be less than 0.0005wt.%C 5alcohol.In one embodiment, ethanol composition comprises 50wppm-1.5wt.%, the branched-chain alcoho of such as 100wppm-1wt.%.In one embodiment, these branched-chain alcohos do not comprise Virahol.Give the example weight percentage ratio of each component in table 7.
In other embodiments, ethanol composition comprises the metal (if any) of very low amounts, and such as ethanol composition of the present invention does not comprise metal substantially.Such as, in one embodiment, ethanol composition of the present invention comprises and is less than 10wppm, such as, be less than 1wppm, be less than 0.1wppm or be less than the copper of 0.05wppm.In one embodiment, ethanol composition does not comprise copper substantially, and preferably, ethanol composition does not comprise copper.In one embodiment, ethanol composition of the present invention does not comprise heavy metal substantially.
In one embodiment, ethanol composition comprises the inorganics of very low amounts.Such as, ethanol composition can comprise and be less than 20mg/L, such as, be less than 10mg/L, be less than 8mg/L or be less than the chlorine/muriate of 5mg/L.With regard to PPM, ethanol composition can comprise and be less than 40wppm, such as, be less than 20wppm or be less than the chlorine/muriate of 10wppm.In one embodiment, ethanol composition does not comprise chlorine substantially, and preferably, ethanol composition does not comprise chlorine.
In one embodiment, ethanol composition comprises and is less than 50wppm, such as, be less than 30wppm, be less than 10wppm, be less than 7wppm, be less than 5wppm or be less than the sulphur of 3wppm.In one embodiment, ethanol composition does not comprise sulphur substantially, and preferably ethanol composition does not comprise sulphur.In one embodiment, ethanol composition can comprise and be less than 10wppm, such as, be less than 4wppm, be less than 3wppm, be less than 2wppm or be less than the vitriol of 1wppm.In one embodiment, ethanol composition does not comprise vitriol substantially, and preferably, ethanol composition does not comprise vitriol.
In one embodiment, ethanol composition comprises and is less than 2mg/L, such as, be less than 1mg/L, be less than 0.5mg/L, be less than 0.3mg/L, be less than 0.2mg/L or be less than the phosphorus of 0.1mg/L.In one embodiment, ethanol composition does not comprise phosphorus substantially, and preferably, ethanol composition does not comprise phosphorus.
In one embodiment, ethanol composition has 6.0-9.5, the pHe of such as 6.5-9.0.In one embodiment, ethanol composition has and is less than 0.01wppm, such as, be less than the total acidity (total acidity) (with acetometer) of 0.007wppm.In one embodiment, ethanol composition has and is less than 65mg/L, such as, be less than 56mg/L or be less than the total acidity (with acetometer) of 30mg/L.
In another embodiment, ethanol composition comprises at least one original position denaturing agent, such as, with the denaturing agent that ethanol cooperatively produces.In these cases, can think that this ethanol composition is " Denatured alcohol composition ".Preferably, Denatured alcohol composition does not comprise is not the denaturing agent prepared by hydrogenation reaction original position.In one embodiment, Denatured alcohol composition does not comprise ex situ denaturing agent substantially.Because provide denaturing agent by building-up reactions, so this Denatured alcohol composition does not advantageously need other (external) denaturing agent to form Denatured alcohol composition when synthesizing.Consequently, this Denatured alcohol composition is suitable for commercial use when synthesizing, such as, be suitable as Denatured alcohol composition and carry out carrying and add or process without other.
Any component discussed herein, percentage ratio or physical/chemical performance are applicable to the ethanol composition of any expection embodied herein.
Finished product ethanol composition disclosed herein is applicable to the various application comprising fuel.In fuel applications, the denaturing agent of finished product ethanol composition and permission is concocted to form fuel ethanol composition of the present invention disclosed herein.Can subsequently by the fuel ethanol composition that so produces and gasoline or diesel oil fuel, such as, carry out concocting for Motor vehicles such as automobile, ship, truck, marine ship, locomotive and small-sized piston engine aircraft at terminal loading frame.
In the U.S., in order to observe current regulation, the fuel denaturing agent of finished product ethanol composition with at least permission of 1.96vol.% is concocted.The fuel denaturing agent of the permission that maximum qualified (conforming) measures current be 5vol.%.As implied above, the denaturing agent allowed according to ASTM D4806 is limited to natural gasoline, gasoline blending stock and white gasoline.Suitable blending stock includes but not limited to alkylide stream, catalytically cracked gasoline stream (such as cracking naphtha); Aromatics saturated vapor oil flow, light straight-run spirit stream, heavy straight-run gasoline stream, dehexanizing column tower bottoms stream, dehexanizing column overhead product (tower top) stream, hydrocracking device topping light naphthar, reformate, toluene and butane stream.
In one embodiment, ethanol composition of the present invention is the component of fuel composition.As an example, fuel composition can comprise fuel element and ethanol of the present invention, and it can comprise the Virahol of institute's discussion amount herein, the Virahol that such as original position is formed.In some embodiments, fuel composition comprises the alcohol that ex situ is formed, such as, joined in fuel composition by external alcohol.In one embodiment, fuel composition comprises the Virahol of original position formation and the Virahol of ex situ formation simultaneously, such as external Virahol.The Virahol that the original position that conventional ethanol composition does not comprise open amount is herein formed.
The production of dehydrated alcohol
Referring now to accompanying drawing 4A and 4B.If should be required to meet the specification of fuel ethanol, those of such as ASTM 4806-11, or other local requirement, can process substantially shift out water from it further by the 3rd overhead product in pipeline 119.This processes further to cause and forms dehydrated alcohol product stream, such as dehydrated alcohol composition.In one embodiment, this processes further and uses one or more separating unit, such as water trap.The example of Suitable dehydration device comprises extractive distillation tower 122(as shown in accompanying drawing 4A); Mol sieve unit 124(is as shown in accompanying drawing 4B); And/or siccative (not shown).Such as, useful dewatering and/or unit comprise U.S. Patent No. 4, and 465,875; 4,559,109; 4,654,123; With 6,375, in 807 discuss those.By reference the full text of these patents is incorporated to herein at this.
Typically, the water in the 3rd overhead product and ethanol form water/ethyl alcohol azeotropy article.In one embodiment, water removes from the water/ethyl alcohol azeotropy article the 3rd overhead product by water trap of the present invention.Such as, dehydration can remove at least 50wt.% from the 3rd overhead product, the water of such as at least 75wt.%, at least 90wt.%, at least 95wt.% or at least 99wt.%.With regard to scope, dewater from the 3rd overhead product and remove 50wt.%-100wt.%, the water of such as 75wt.%-99.9999wt.%, 90wt.%-99.999wt.%, 90wt.%-99.99wt.%, 90wt.%-99.9wt.% or 90wt.%-99.5wt.%.This water is removed to cause from the 3rd overhead product and forms dehydrated alcohol composition.
The aqueous streams 128 leaving water trap mainly comprises water, such as at least 50wt.%, the water of such as at least 75wt.%, at least 90wt.%, at least 95wt.% or at least 99wt.%, and preferably it is removed from system 100.In one embodiment, the 4th resistates 128 part can be turned back to the arbitrary portion of system 100.In preferred embodiments, water in any one of tower, such as, can be used as extraction agent in the second tower 108.
In accompanying drawing 4A, can such as by pipeline 119 by the overhead product comprising ethanol/water azeotrope from the 3rd tower 109 to entering the 4th tower 122(also referred to as " treating tower (finishingcolumn) ") in.Water is isolated from the water/ethyl alcohol azeotropy article the 3rd overhead product and is such as distilled out by the 4th tower 122 further.Consequently, the ethanol of dehydration further reclaims as the 4th overhead product in pipeline 126 by the 4th tower 122.
Preferably, the 4th tower 122 is the extractive distillation towers using extraction agent and preferably under atmospheric pressure operate.Extractive distillation is gas-liquid separation process, and it uses other component to improve the relative volatility of component to be separated.In extractive distillation, use and there is optionally high boiling solvent, to change activity quotient, and therefore improve the separation factor of component.Other component can be mixture or the hyperbranched polymer of liquid solvent, ionic liquid, dissolved salt, volatile liquid solvent and dissolved salt.
4th tower 122 preferably comprises 1-150 column plate, such as 10-100 or 20-70 column plate.As indicated above, column plate can be sieve plate, fixed float valve plate, mobile valve tray or other suitable design any known in the art.Exemplary extraction agent can include but not limited to ethylene glycol, glycerine, gasoline and hexane.The 3rd overhead product in pipeline 119 can be incorporated into the 4th tower 122 at any height (level).Preferably, by the middle portion of pipeline 119 at the 4th tower 122, such as, in the middle of, 1/2nd or middle 1/3rd introduce in the 4th tower 122.
In one embodiment, as shown in accompanying drawing 4B, by from the 3rd tower 109 overhead product to enter comprise molecular sieve mol sieve unit 124 in.In these embodiments, molecular sieve isolates other water from the 3rd overhead product pipeline 119.In some embodiments, mol sieve unit 124 may be used for substitution of refined tower or with treating tower coupling (conjunction).Generally speaking, molecular sieve can be configured in molecular sieve bed (not shown).In one embodiment, select to remove one or more impurity that may be present in the 3rd overhead product to molecular sieve.Choice criteria can comprise such as hole size and bulk properties.In one embodiment, molecular screen material selected to remove water, acetic acid and/or ethyl acetate from the 3rd overhead product thus form dehydrated alcohol composition.Suitable molecular sieve comprises such as zeolite and molecular sieve 3a, 4A and 5A(be purchased from Aldrich).In another embodiment, inorganic adsorbent such as lithium chloride, silica gel, activated alumina and/or bio-based sorbent material such as hominy grits can be used.In preferred embodiments, the water of amount mentioned above removes from the 3rd overhead product by mol sieve unit 124.
In addition, can use other separating unit, such as dewatering unit, as desiccant system and/or membranous system, substitutes or coupling treating tower mentioned above and/or mol sieve unit.If use multiple dewatering unit, then can use the dewatering unit of identical or different type by arbitrary disposition.Preferably, extractive distillation tower and membranous system each other together with use.Optionally, in treating tower, such as, use molecular sieve with bed at an upper portion thereof.
Other example dehydration method comprises component distillation and membrane sepn.In component distillation, volatile constituent (being often called entrainer) is joined in component to be separated.Adding of entrainer defines azeotrope with described component, therefore changes their relative volatility.Consequently, the separation factor (activity quotient) of described component is improved.In one embodiment, component distillation system comprises one or more distillation tower, such as two or more or three or more distillation towers.
Membrane sepn such as film pervasion evaporation also can be for separating of the effective of azeotropic mixture and power-economizing method.Generally speaking, pervaporation is based on solution diffusion mechanism, and it depends on the gradient of the partial potential between charging and the permeate side of film.In one embodiment, film can be wetting ability or hydrophobicity.Preferably, due to the less molecular dimension of water, film is that wetting ability or selectivity are through water (water permselective).In other embodiments, film is that hydrophobicity or selectivity are through ethanol.Typically, three class films can be used, i.e. mineral membrane, polymeric film and composite membrane.
Dehydrated alcohol composition
Dehydrated alcohol composition advantageously comprises the ethanol and (if any) a small amount of water that are formed preferably by acetic acid hydrogenation of the present invention and separating step.In one embodiment, as used herein term " dehydrated alcohol composition " refers to anhydrous ethanol composition substantially.The total weight that such as anhydrous ethanol composition can have based on this essentially no water-ethanol composition is substantially less than 1wt.%, such as, be less than 0.5wt.%, be less than 0.1wt.%, be less than 0.01wt.%, be less than 0.001wt.% or be less than the water-content of 0.0001wt.% water.Table 8 provides the exemplary range of water concentration in dehydrated alcohol composition.Although table 8 demonstrates in other embodiments, water is preferably to exist on a small quantity, and dehydrated alcohol composition can be completely anhydrous, such as, not containing detectable water.In these cases, the conventional water detection method used in industry can be utilized to measure water-content or not have water.Preferably, dehydrated alcohol composition comprises at least 95wt.%, the ethanol of such as at least 95wt.%, at least 99wt.%, at least 99.9wt.% or at least 99.99wt.%.Table 6 provides the exemplary range of alcohol concn in dehydrated alcohol composition.
Except the water that ethanol and (if any) are a small amount of, dehydrated alcohol composition can also comprise other impurity such as acetic acid of only trace; C 3alcohol is as n-propyl alcohol; And/or C 4-C 5alcohol.The exemplary compositing range of various impurity providing ethanol, water and may exist with a small amount of (if any) in following table 8.
In other embodiments, ethanol composition comprises the metal (if any) of very low amounts, and such as ethanol composition of the present invention does not comprise metal substantially.Such as, in one embodiment, ethanol composition of the present invention comprises and is less than 10wppm, such as, be less than 1wppm, be less than 0.1wppm or be less than the copper of 0.05wppm.In one embodiment, ethanol composition of the present invention does not comprise heavy metal substantially.
In one embodiment, ethanol composition comprises the inorganics of very low amounts.Such as, ethanol composition can comprise and be less than 10mg/L, such as, be less than 8mg/L or be less than the chlorine/muriate of 5mg/L.With regard to PPM, ethanol composition can comprise and be less than 40wppm, such as, be less than 20wppm or be less than the chlorine/muriate of 10wppm.In one embodiment, ethanol composition comprises and is less than 30wppm, such as, be less than 10wppm, be less than 7wppm, be less than 5wppm or be less than the sulphur of 3wppm.Such as, ethanol composition can comprise and be less than 4wppm, such as, be less than 3wppm, be less than 2wppm or be less than the vitriol of 1wppm.In one embodiment, ethanol composition comprises and is less than 0.5mg/L, such as, be less than 0.3mg/L, be less than 0.2mg/L or be less than the phosphorus of 0.1mg/L.
Dehydrated alcohol composition of the present invention preferably containing very low amounts, such as, is less than other alcohol of 0.5wt.%, such as methyl alcohol, butanols, isopropylcarbinol, primary isoamyl alcohol and other C 4-C 20alcohol.
The dehydrated alcohol composition of embodiment of the present invention goes for the various application comprising fuel.In fuel applications, as mentioned above the denaturing agent of dehydrated alcohol composition and permission can be concocted, more such as carry out concocting for Motor vehicles such as automobile, ship, truck, marine ship, locomotive and small-sized piston engine aircraft at terminal loading frame and gasoline or diesel oil fuel subsequently.
In the U.S., in order to observe current regulation, the fuel denaturing agent of dehydrated alcohol composition with at least permission of 1.96vol.% is concocted.The fuel denaturing agent of the permission of maximum qualified amount current be 5vol.%.As implied above, the denaturing agent allowed according to ASTM D4806 is limited to natural gasoline, gasoline blending stock and white gasoline.Suitable blending stock includes but not limited to alkylide stream, catalytically cracked gasoline stream (such as cracking naphtha); Aromatics saturated vapor oil flow, light straight-run spirit stream, heavy straight-run gasoline stream, dehexanizing column tower bottoms stream, dehexanizing column overhead product (tower top) stream, hydrocracking device topping unit light naphthar, reformate, toluene and butane stream.
Fuel ethanol composition produced according to the invention can meet the standard specifications (StandardSpecifcation for Denatured Fuel Ethanol fr Blending with Gasolinesfr Use as Automotive Spark Ignition Engine Fuel) of the fuel ethanol for being used as automobile fuels for spark ignition engines with gasoline concoction, ASTM D4806-11, gives its performance requriements in following table 9.
In one embodiment, blending of fuel ethanol composition comprises the metal (if any) of very low amounts, and such as blending of fuel ethanol composition does not comprise metal substantially.In another embodiment, blending of fuel ethanol composition does not comprise heavy metal substantially.Such as in one embodiment, blending of fuel ethanol composition is substantially free of lead, comprises and is less than 20mg/1, such as, be less than 15mg/1, be less than 10mg/1 or be less than the lead of 5mg/1.In one embodiment, blending of fuel ethanol composition is substantially free of manganese.Such as, blending of fuel ethanol composition comprises and is less than 10mg/1, the manganese being such as less than 6mg/1, being less than 3mg/l, being less than 1mg/1.In one embodiment, blending of fuel ethanol composition is substantially free of copper.Such as, blending of fuel ethanol composition comprises and is less than 0.5mg/kg copper, or is less than 0.3mg/kg copper, or is less than 0.1mg/kg copper.In one embodiment, blending of fuel ethanol composition is substantially free of the combination of sodium and potassium.Such as, blending of fuel ethanol composition comprises and is less than 10mg/kg, such as, be less than 8mg/kg, be less than 5mg/kg or be less than the sodium of 2mg/kg and the combination of potassium.In one embodiment, blending of fuel ethanol composition is substantially free of the combination of calcium and magnesium.Such as, blending of fuel ethanol composition comprises and is less than 15mg/kg, such as, be less than 10mg/kg, be less than 5mg/kg or be less than the calcium of 2mg/kg and the combination of magnesium.In another embodiment, blending of fuel ethanol composition is substantially free of aluminium and silicon.Such as, blending of fuel ethanol composition comprises and is less than 60mg/kg, such as, be less than 50mg/kg, be less than 25mg/kg, be less than 10mg/kg or be less than the aluminium of 5mg/kg and the combination of silicon.In another embodiment, blending of fuel ethanol composition is substantially free of sodium.Such as, blending of fuel ethanol composition comprises and is less than 150mg/kg, such as, be less than 100mg/kg, be less than 50mg/kg or be less than the sodium of 10mg/kg.In one embodiment, blending of fuel ethanol composition is substantially free of vanadium.Such as, blending of fuel ethanol composition comprises and is less than 400mg/kg, such as, be less than 350mg/kg, be less than 200mg/kg or be less than the vanadium of 150mg/kg.In another embodiment, blending of fuel ethanol composition is substantially free of calcium.Such as, blending of fuel ethanol composition comprises and is less than 50mg/kg, such as, be less than 30mg/kg, be less than 15mg/kg or be less than the calcium of 10mg/kg.In another embodiment, blending of fuel ethanol composition is substantially free of zinc.Such as, blending of fuel ethanol composition comprises and is less than 25mg/kg, such as, be less than 15mg/kg or be less than the zinc of 10mg/kg.
In order to more effectively understand invention disclosed herein, provide non-limiting embodiments below.Embodiment describes each embodiment of ethanol composition of the present invention below.
Embodiment
Embodiment 1
Use above-mentioned method of hydrotreating and separation method, prepare some ethanol composition.In the medial temperatures of 291 DEG C and 2, under the top hole pressure of 063KPa, produce by the gasification feed and hydrogen reaction that make to comprise 95.2wt.% acetic acid and 4.6wt.% water in the presence of a catalyst the crude ethanol product comprising ethanol, acetic acid, water and ethyl acetate, described catalyzer comprises the 1.6wt.% platinum of load on the Calucium Silicate powder improved silica extrudate of 1/8 foot and 1wt.% tin.The entrance that reactor is got back in unreacted hydrogen recirculation is made at 3,893hr -1gHSV under total H 2/ acetic acid mol ratio is 5.8.Use the separation scheme purification of crude ethanol product as shown in Figure 1 with distillation tower.
Table 10 shows the composition data of these ethanol composition.Term " C as used in this article 2+alcohol " relate to the alcohol had more than 2 carbon atoms.
Comparative example A
Table 11 shows the data by the standby contrast ethanol composition of sugarcane fermentation.
Comparative example B
Table 12 shows the data of the contrast ethanol composition by molasses fermented preparation.
Comparative example C
Table 13 shows the data of the contrast ethanol composition prepared by Fiscber-Tropscb synthesis.
Unexpected and unexpectedly, in embodiment 1, the amount of Virahol is than the height in comparative example A-C.In addition, in embodiment 1, the amount of methyl alcohol advantageously can't detect.On the contrary, in comparative example A-C, the amount of methyl alcohol is significantly higher, such as 42wppm-51wppm.
Embodiment 2
By above discuss and prepare crude ethanol product sample by acetic acid hydrogenation.This sample comprises ethanol, acetic acid, acetaldehyde, water and ethyl acetate.
Use the first tower, the second tower and the 3rd tower that often kind of crude ethanol product sample is carried out purifying as illustrated in figure 1a.In each case, the 3rd overhead product obtained from respective crude ethanol product sample is analyzed.The average composition value of the 3rd overhead product is provided in table 14.
3rd overhead product, when by above discuss dewater time, the dehydrated alcohol composition with the average composition value provided in table 15 is provided.As shown in table 15, the dehydrated alcohol composition formed by acetic acid hydrogenation of the present invention and separating step comprises the ethanol water a small amount of with (if any).
Although describe the present invention in detail, various amendments within the spirit and scope of the present invention will be apparent to those skilled in the art.In view of the above discussion, above about background technology with describe this area relevant knowledge of discussing and reference in detail, by reference their disclosure is all incorporated to herein.In addition, should understand and can partly or entirely carry out combining or exchanging in the various piece of all respects of the present invention hereafter and/or in the dependent claims quoted from and multiple embodiment and multiple feature.In the description of each embodiment aforementioned, as those skilled in the art can recognize, those embodiments quoting another embodiment suitably can combine with other embodiment.In addition, those skilled in the art will recognize that aforementioned description is only way of example, and be not intended to limit the present invention.

Claims (75)

1., for the fuel ethanol composition with blending of fuel, described composition comprises:
Contain the ethanol composition of at least 92wt.% ethanol, 95wppm-850wppm Virahol and n-propyl alcohol; With
At least 1.96vol.% fuel denaturing agent;
Wherein the weight ratio of Virahol and n-propyl alcohol is at least 0.5:1.
2. the fuel ethanol composition of claim 1, wherein said fuel denaturing agent is selected from natural gasoline, gasoline blending stock and white gasoline.
3. the fuel ethanol composition of claim 1, also comprises the water being less than 1vol.%.
4. the fuel ethanol composition of claim 3, in wherein said ethanol composition, the weight ratio of Virahol and water is 1:80-1:1000.
5. the fuel ethanol composition of claim 1, wherein said ethanol composition also comprises the acetaldehyde being less than 10wppm.
6. the fuel ethanol composition of claim 1, wherein said ethanol composition also comprises the diethyl acetal being less than 10wppm.
7. the fuel ethanol composition of claim 1, wherein said ethanol composition also comprises the C being less than 300wppm 4-C 5alcohol.
8. the fuel ethanol composition of claim 1, wherein said ethanol composition also comprises the n-propyl alcohol of 95wppm-270wppm.
9. the fuel ethanol composition of claim 1, wherein said ethanol composition is not containing benzene.
10. the fuel ethanol composition of claim 1, wherein said ethanol composition is not containing methyl alcohol.
The fuel ethanol composition of 11. claims 1, wherein said ethanol composition is not containing C 5alcohol.
The fuel ethanol composition of 12. claims 1, wherein said ethanol composition is not obtained by fermentation.
The fuel ethanol composition of 13. claims 1, wherein this ethanol composition is not chloride.
The fuel ethanol composition of 14. claims 1, wherein this ethanol composition comprises the chlorine being less than 40wppm.
The fuel ethanol composition of 15. claims 1, wherein said ethanol composition not cupric.
The fuel ethanol composition of 16. claims 1, wherein said ethanol composition comprises the copper being less than 10wppm.
The fuel ethanol composition of 17. claims 1, wherein said ethanol composition not sulfur-bearing.
The fuel ethanol composition of 18. claims 1, wherein said ethanol composition comprises the sulphur being less than 50wppm.
The fuel ethanol composition of 19. claims 1, wherein said ethanol composition not containing sulfate.
The fuel ethanol composition of 20. claims 1, wherein said ethanol composition comprises the vitriol being less than 10wppm.
The fuel ethanol composition of 21. claims 1, wherein said ethanol composition is not phosphorous.
The fuel ethanol composition of 22. claims 1, wherein said ethanol composition comprises the phosphorus being less than 2 mg/litre.
The fuel ethanol composition of 23. claims 1, wherein blending of fuel ethanol composition is not leaded.
The fuel ethanol composition of 24. claims 1, wherein blending of fuel ethanol composition comprises the lead being less than 15mg/l.
The fuel ethanol composition of 25. claims 1, wherein blending of fuel ethanol composition comprises the lead being less than 5mg/l.
The fuel ethanol composition of 26. claims 1, wherein blending of fuel ethanol composition comprises the manganese being less than 10mg/l.
The fuel ethanol composition of 27. claims 1, wherein blending of fuel ethanol composition comprises the manganese being less than 1mg/l.
The fuel ethanol composition of 28. claims 1, it is not containing heavy metal.
The fuel ethanol composition of 29. claims 1, wherein blending of fuel ethanol composition comprises the copper being less than 0.5mg/kg.
The fuel ethanol composition of 30. claims 1, wherein blending of fuel ethanol composition comprises the copper being less than 0.1mg/kg.
The fuel ethanol composition of 31. claims 1, wherein blending of fuel ethanol composition comprises the sodium and potassium that are altogether less than 8mg/kg.
The fuel ethanol composition of 32. claims 1, wherein blending of fuel ethanol composition comprises the sodium and potassium that are altogether less than 5mg/kg.
The fuel ethanol composition of 33. claims 1, wherein blending of fuel ethanol composition comprises the calcium and magnesium that are altogether less than 10mg/kg.
The fuel ethanol composition of 34. claims 1, wherein blending of fuel ethanol composition comprises the calcium and magnesium that are altogether less than 5mg/kg.
The fuel ethanol composition of 35. claims 1, wherein blending of fuel ethanol composition comprises the aluminium and silicon that are altogether less than 60mg/kg.
The fuel ethanol composition of 36. claims 1, wherein blending of fuel ethanol composition comprises the aluminium and silicon that are altogether less than 25mg/kg.
The fuel ethanol composition of 37. claims 1, wherein blending of fuel ethanol composition comprises the sodium being less than 150mg/kg.
The fuel ethanol composition of 38. claims 1, wherein blending of fuel ethanol composition comprises the sodium being less than 100mg/kg.
The fuel ethanol composition of 39. claims 1, wherein blending of fuel ethanol composition comprises the vanadium being less than 400mg/kg.
The fuel ethanol composition of 40. claims 1, wherein blending of fuel ethanol composition comprises the vanadium being less than 350mg/kg.
The fuel ethanol composition of 41. claims 1, wherein blending of fuel ethanol composition comprises the calcium being less than 50mg/kg.
The fuel ethanol composition of 42. claims 1, wherein blending of fuel ethanol composition comprises the calcium being less than 30mg/kg.
The fuel ethanol composition of 43. claims 1, wherein blending of fuel ethanol composition comprises the zinc being less than 25mg/kg.
The fuel ethanol composition of 44. claims 1, wherein blending of fuel ethanol composition comprises the zinc being less than 15mg/kg.
The fuel ethanol composition of 45. claims 1, wherein said ethanol composition has the pH of 6-9.5.
The fuel ethanol composition of 46. claims 1, wherein said ethanol composition have be less than 0.01wppm with the total acidity of acetometer.
The fuel ethanol composition of 47. claims 1, wherein said ethanol composition comprises and is less than the alcohol of 350wppm except ethanol.
48. fuel ethanol compositions as claimed in claim 1, wherein said ethanol composition is derived from the hydrogenation of acetic acid.
The fuel ethanol composition of 49. claims 48, wherein said acetic acid is formed by methyl alcohol and carbon monoxide, wherein methyl alcohol, carbon monoxide and for the hydrogen of hydrogenation step separately derived from synthetic gas, and the wherein said syngas-derived carbon source from being selected from Sweet natural gas, oil, oil, coal, biomass and their combination.
The fuel ethanol composition of 50. claims 1, the fuel wherein for concocting with described fuel ethanol composition is gasoline.
The fuel ethanol composition of 51. claims 1, the fuel wherein for concocting with described fuel ethanol composition is diesel oil fuel.
52. for the fuel ethanol composition with blending of fuel, and described composition comprises:
Ethanol composition, described ethanol composition contains the ethanol of at least 92wt.%, n-propyl alcohol and be selected from least two kinds of other alcohol of Virahol, butanols, 2-butanols and isopropylcarbinol, condition is that described at least two kinds of other alcohol a kind of is Virahol and has the Virahol of at least 95wppm; And
At least fuel denaturing agent of 1.96vol.%,
Wherein said ethanol composition is not containing methyl alcohol; With
Wherein the weight ratio of Virahol and n-propyl alcohol is at least 0.5:1.
The fuel ethanol composition of 53. claims 52, wherein said at least two kinds of other alcohol exist with the amount being less than 1wt.% in described ethanol composition.
The fuel ethanol composition of 54. claims 52, the amount of the Virahol existed in wherein said ethanol composition is less than 850wppm.
The fuel ethanol composition of 55. claims 52, also comprises the water being less than 1vol.%.
The fuel ethanol composition of 56. claims 52, wherein said at least two kinds of other alcohol are the alcohol that original position is formed.
The fuel ethanol composition of 57. claims 52, wherein said ethanol composition is synthesized by acetic acid hydrogenation and purifying, and wherein said Denatured alcohol composition does not comprise ex situ denaturing agent when synthesizing.
The fuel ethanol composition of 58. claims 57, wherein said Denatured alcohol composition is suitable for commercial applications when synthesizing.
The fuel ethanol composition of 59. claims 52, also comprises the other alcohol that one or more are not the alcohol that original position is formed.
The fuel ethanol composition of 60. claims 52, the fuel wherein for concocting with described composition is gasoline.
The fuel ethanol composition of 61. claims 52, the fuel wherein for concocting with described composition is diesel oil fuel.
62. for the fuel ethanol composition with blending of fuel, and described composition comprises:
Ethanol composition, described ethanol composition comprises at least 95wt.% ethanol, at least 95wppm Virahol, and n-propyl alcohol, and wherein the weight ratio of Virahol and n-propyl alcohol is at least 0.5:1; And
At least fuel denaturing agent of 1.96vol.%.
The fuel ethanol composition of 63. claims 62, the Virahol existed in wherein said ethanol composition and the weight ratio of n-propyl alcohol are at least 1:1.
The fuel ethanol composition of 64. claims 62, the amount of the Virahol existed in wherein said ethanol composition is less than 1000wppm.
The fuel ethanol composition of 65. claims 62, the amount of the n-propyl alcohol existed in wherein said ethanol composition is less than 270wppm.
The fuel ethanol composition of 66. claims 62, also comprises the water being less than 1vol.%.
The fuel ethanol composition of 67. claims 62, wherein said Virahol and n-propyl alcohol are the alcohol that original position is formed.
The fuel ethanol composition of 68. claims 67, wherein said ethanol composition is synthesized by acetic acid hydrogenation and purifying, and wherein said Denatured alcohol composition does not comprise ex situ denaturing agent when being formed.
The fuel ethanol composition of 69. claims 68, wherein said Denatured alcohol composition is suitable for commercial applications when being formed.
The fuel ethanol composition of 70. claims 68, also comprises the other alcohol that one or more are not the alcohol that original position is formed.
The fuel ethanol composition of 71. claims 62, the fuel wherein for concocting with described composition is gasoline.
The fuel ethanol composition of 72. claims 62, the fuel wherein for concocting with described composition is diesel oil fuel.
73. for the fuel ethanol composition with blending of fuel, and described composition comprises:
Containing at least 95wt.% ethanol, n-propyl alcohol, at least 95wppm Virahol, be less than the ethanol composition of the acetaldehyde of the amount of 10wppm
Wherein the amount of acetaldehyde is less than the amount of Virahol; With
At least 1.96vol.% fuel denaturing agent,
Wherein the weight ratio of Virahol and n-propyl alcohol is at least 0.5:1.
The fuel ethanol composition of 74. claims 73, wherein said fuel is selected from diesel oil fuel and/or gasoline.
The fuel ethanol composition of 75. claims 73, wherein said fuel denaturing agent is selected from natural gasoline, gasoline blending stock and white gasoline.
CN201180014151.7A 2010-08-06 2011-08-03 Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels Expired - Fee Related CN102811990B (en)

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