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EP2121878A1 - Production d'un mélange d'alcool utilisable dans des véhicules flexibles en carburant via la synthèse de fischer-tropsch - Google Patents

Production d'un mélange d'alcool utilisable dans des véhicules flexibles en carburant via la synthèse de fischer-tropsch

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Publication number
EP2121878A1
EP2121878A1 EP07762313A EP07762313A EP2121878A1 EP 2121878 A1 EP2121878 A1 EP 2121878A1 EP 07762313 A EP07762313 A EP 07762313A EP 07762313 A EP07762313 A EP 07762313A EP 2121878 A1 EP2121878 A1 EP 2121878A1
Authority
EP
European Patent Office
Prior art keywords
composition
butanol
alcohols
gasoline
fuel
Prior art date
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EP07762313A
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German (de)
English (en)
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EP2121878A4 (fr
Inventor
David Bradin
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Individual
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Individual
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Classifications

    • 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
    • C10L1/10—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
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy

Definitions

  • the present invention relates to alternative fuel compositions which comprise ethanol, isopropyl alcohol, and secondary-butanol and/or t-butanol, as well as blends of these compositions with gasoline.
  • Gasoline is derived from crude oil, which is a non-renewable resource of finite supply.
  • Extensive research effort is now being directed toward replacing some or all petroleum-based diesel fuel with gasoline/ethanol blends such as E85 (85% ethanol and 15% gasoline by volume).
  • E85 suffers from a significant loss (roughly 20%) in energy per unit volume relative to gasoline.
  • flexible fuel vehicles can run efficiently on these fuels, and the high oxygenate content makes them very clean burning fuels.
  • n-butanol provides sufficient power to run a normal gasoline engine.
  • the use of n-butanol as a viable energy source is not without its problems. Much like ethanol oxidizes to acetic acid, n-butanol oxidizes to butyric acid, which has a very strong and offensive odor. Also, there is a finite amount of feedstock to produce fermentable materials such as n-butanol.
  • sugar can be fermented, but it is difficult and expensive to convert lignocellulosic materials to the component parts, such as lignin, cellulose, and hemicellulose, and to then depolymerize the cellulose and/or hemicellulose to the component sugars. Further, fermentation produces a significant amount of carbon dioxide.
  • Fischer- Tropsch synthesis has been used to convert coal and natural gas, available domestically, into distillate fuels. More recently, biomass, including lignin, sugars, cellulose, and the like, has been converted to syngas for use in Fischer-Tropsch synthesis. When catalysts with high chain growth probabilities are used, the products are primarily paraffin wax and water. The paraffin wax is typically hydrocracked to form fuel products.
  • the products tend to include a carbon dioxide, unreacted syngas, and low molecular weight (C 2-4 ) paraffins and olefins, in addition to some products in the gasoline and diesel ranges.
  • C 2-4 low molecular weight paraffins and olefins
  • Alternative fuel compositions blends of the alternative fuel compositions and gasoline, and methods for their preparation and use are disclosed.
  • the alternative fuel compositions comprise ethanol, n-propyl and/or isopropyl alcohol, and n-butanol, sec-butanol and/or t-butanol.
  • methanol is substantially absent from the composition.
  • substantially absent is meant less than 10% by volume, ideally less than 5% by volume, and, more ideally, less than 1% by volume.
  • the fuel compositions are prepared by first conducting Fischer- Tropsch synthesis using a catalyst with low chain growth possibilities to produce a product stream which comprises C2-4 olefins, and subjecting the olefins to hydrolysis conditions, which add water across the double bonds.
  • the hydrolysis is typically done with an acid catalyst, and the resulting C 3 and C 4 alcohols are therefore primarily secondary or tertiary alcohols.
  • Fischer-Tropsch chemistry performed using an iron catalyst, or other catalyst with low chain growth probabilities, tends to provide a variety of gaseous and liquid products, including unreacted synthesis gas, methane, and C 2 - 4 hydrocarbons (a mixture of olefins and paraffins).
  • synthesis gas methane
  • C 2 - 4 hydrocarbons a mixture of olefins and paraffins.
  • Typical, about 75% of the C2-8 products from Fischer-Tropsch synthesis are normal alpha-olefms (NAOs), and the gases are typically separated from the liquid products (see, for example, U.S. Patent No. 6,849,774, the contents of which are hereby incorporated by reference).
  • the methane and other light paraffins can be recycled through an upstream synthesis gas generator, but the light olefins must be separated from the light paraffins in order to do this.
  • the olefins and paraffins have very similar boiling points.
  • Prior art approaches for separating the olefins from the paraffins involve relatively expensive cryogenic distillation.
  • the processes described herein convert the olefins to alcohols, optionally in the presence of the methane and paraffins. Since the alcohols have significantly higher boiling points than the paraffins, this enables facile separation of olefins (when converted to the resulting alcohols) from paraffins.
  • the other light paraffins i.e., C 2 - 4 paraffins
  • the alcohols can be produced by olefin hydrolysis, by fermentation, by hydro formylation of the C2-4 olefin products of Fischer-Tropsch synthesis, and by conducting Fischer- Tropsch synthesis in a way that maximizes alcohol formation. That is, normal straight chain alcohols can be formed during Fischer-Tropsch synthesis under certain conditions, and if they do not dehydrate under the Fischer-Tropsch conditions, they can be isolated (often in yields approximating 60%).
  • the chemistry described herein can be combined with one or more products resulting from fermentation chemistry, such as ethanol and/or n-butanol, to produce a variety of alcoholic fuel mixtures that can be used alone, or in combination with gasoline.
  • the alcoholic mixture produced using the processes described herein includes sufficient C3 and C 4 alcohols, and, optionally, Cs_8 alcohols, such that the alcohol blend has approximately the same, and, ideally, more, energy per unit volume than E85, even without the addition of gasoline. That is, butanols (n-butanol, sec-butanol, and t-butanol) have approximately the same energy per unit volume as gasoline. So, a mixture comprising ethanol, isopropyl alcohol, and sec-butanol and/or t-butanol, where the butanols are present in at least 15% by volume, will have at least the same energy per unit volume as E85.
  • isopropyl alcohol has energy per unit volume between that of ethanol and butanol
  • the presence of isopropyl alcohol in combination with the sec-butanol and/or t-butanol also results in at least equivalent energy per unit volume to E85, even if the butanol content is less than at least 15% by volume.
  • the alcohol blends can further be combined with conventional gasoline, thereby increasing the energy per unit volume.
  • the composition comprises between about 5 and 45% by volume of sec-butanol and/or t-butanol, between about 5 and about 45% isopropyl alcohol, between about 5 and about 80% by volume ethanol, and between about 0 and about 25% Cs_8 alcohols.
  • Blends of this alcoholic composition with gasoline, where the ratio of the alcoholic composition to gasoline range from 1 :99 to 99:1, are also disclosed.
  • the alternative fuel can also be a gasoline/alcohol blend, where the alcohol comprises a) ethanol b) n-propanol and/or isopropyl alcohol, and c) n-butanol, sec-butanol, or t-butanol, where the alcohols are present in amounts up to about 95 percent by volume of the gasoline/alcohol blend.
  • gasoline is blended with between about 5 and about 85 percent by volume of the alcoholic mixtures described herein, and between about 5 and 85 percent by volume of gasoline.
  • the olefins can be derived, in whole or in part, by Fischer- Tropsch synthesis on syngas formed using, for example, coal, glycerol, ethanol, methanol, methane, lignin, cellulose, hemicellulose, black liquor, or biomass (including corn stover, switchgrass, bagasse, sawdust, recycled paper, and the like) as a starting material.
  • the olefin hydrolysis can be run at substantially quantitative yields, and adds significantly to the total weight of the product.
  • fuel products that burn in flexible fuel vehicles can be obtained in significant yields from Fischer-Tropsch reactors, using relatively inexpensive iron-containing catalysts, without the need for a hydrocracker (such as is used to crack Fischer-Tropsch wax).
  • Product yields are improved, relative to the volume of the olefins produced, by the addition of water across the double bond. Further, the resulting product is more stable than the olefins, which are otherwise prone to polymerization or other further reactions.
  • the separation of C2-4 alkanes from C 2 - 4 alcohols is significantly easier than the separation of C 2 - 4 alkanes from C 2 - 4 olefins.
  • the cost of setting up the plant is significantly reduced by using a combination of relatively inexpensive Fischer-Tropsch catalysts and conditions, and relatively inexpensive (compared with a hydrocracker) olefin hydrolysis reactor.
  • the amount of water present in the hydrolysis reaction is significantly less than that present in a fermentation plant, so distillation costs are relatively lower.
  • the fuel compositions described herein can be blended with biofuels such as ethanol and "biobutanol" (n-butanol derived by fermentation) to maximize the yield of alternative fuels that run on flexible fuel vehicles.
  • olefin hydrolysis tends to form secondary and/or tertiary alcohols, which do not oxidize to corrosive and odiferous carboxylic acids such as butyric acid.
  • E85 which requires gasoline to work in a flexible fuel vehicle
  • the presence of higher molecular weight alcohols means that the fuel can work in flexible fuel vehicles without adding any gasoline.
  • the presence of higher molecular weight alcohols means that the fuel can be used in conventional gasoline engines at higher concentrations than ethanol (i.e., at concentrations greater than 5% by volume, ideally up to or greater than 10% by volume).
  • the resulting alternative fuel can be derived, at least in part, from renewable resources, in that the syngas can be derived from renewable resources, and a significant portion of the molecule comes from the water used to hydro lyze the olefins.
  • the alternative fuel compositions, and blends thereof with gasoline, can help reduce U.S. dependence on foreign crude oil.
  • An alternative fuel composition that comprises C2-4 alcohols, ideally with at least a portion of the C3 and C 4 alcohols being secondary or tertiary alcohols, are disclosed. Blends of the fuel composition with gasoline, and methods of making and using the composition and blends thereof, are also disclosed.
  • the processes described herein are integrated processes.
  • integrated process refers to a process which involves a sequence of steps, some of which may be parallel to other steps in the process, but which are interrelated or somehow dependent upon either earlier or later steps in the total process.
  • alkyl refers to a saturated straight, branched, or cyclic hydrocarbon of C 1-6 , and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, cyclopentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl.
  • olefin refers to an unsaturated straight, branched or cyclic hydrocarbon of C 2-10 , and specifically includes ethylene, propylene, butylene, isobutylene, pentene, cyclopentene, isopentene, hexene, cyclohexene, 3- methylpentene, 2,2-dimethylbutene, 2,3-dimethylbutene, 1-heptene, 2-heptene, 3- heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, A- nonene, 1-decene, 2-decene, 3-decene, 4-decene, and 5-decene.
  • Ethylene, propylene and isobutylene can be preferred due to their relatively low cost, and C 2 - 8 olefins can be preferred as they are produced as the major products in Fischer-
  • Highly substituted olefins can be preferred, because they can stabilize a carbocation intermediate more readily than unsubstituted olefins, and thus facilitate olefin hydrolysis to form alcohols.
  • the alcohols described herein are a blend comprising, and in one embodiment, consisting essentially of, C2-4 alcohols. Higher molecular weight alcohols can also be present. Methanol can be present, but since it has a relatively low energy per unit volume, is not a preferred component, and is ideally substantially absent (i.e., less than about 3% by volume, preferably less than about 1% by volume) from the composition. Cs + alcohols can be present, although it is preferred that the alcohols not exceed C 10 (i.e., that less than 5% of the composition is C 10+ ). More ideally, the amount of C2-4 alcohols is between about 60 and about 80 percent of the alcohols, and even more ideally, is greater than 90 percent of the alcohols, by volume.
  • alcohols are present in a fuel composition
  • a fuel composition comprising a mixture of ethanol, isopropanol, and one or more alcohols selected from the group consisting of sec- butanol and t-butanol.
  • the composition can further comprise n-propanol.
  • the composition comprises less than 10% of alcohols with a molecular weight greater than butanol, and comprises at least 15%, preferably at least 25%, more preferably, at least 30% sec-butanol and/or t-butanol by volume.
  • the energy content of the fuel composition meets or exceeds that of ASTM D5798-99 (Standard Specification for Fuel Ethanol for Automotive Spark-Ignition Engines).
  • the composition is preferably substantially devoid (i.e., less than 3%) of each of n-butanol and methanol, and in another aspect, the composition includes less than 5% n-butanol.
  • the composition can be produced by converting syngas to a C 2 - 4 olefm-containing product stream using Fisher-Tropsch synthesis, and subjecting all or a portion of the C2-4 olefins to olefin hydrolysis.
  • the C3 + alcohols be secondary or tertiary alcohols, but these can be preferred, as it can be desired to minimize the ability of the alcohols to oxidize to carboxylic acids, which acids can be undesirable due to their corrosiveness and/or odor.
  • Any alcohol that provides a fuel composition with sufficient energy for use in gasoline or flexible fuel engines can be used to prepare either the fuel compositions.
  • Suitable alcohols for use in the present invention include, but are not limited to, saturated straight, branched, or cyclic alcohols of C 1-6 , and specifically include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, cyclopentanol, isopentanol, neopentanol, hexanol, isohexanol, cyclohexanol, 3-methylpentanol, 2,2-dimethylbutanol, and 2 , 3 -dimethy lbutano 1.
  • Ethanol is generally available commercially in a denatured form, for example, grade 3 A, which contains minor amounts of methanol and water.
  • the ethanol can be that which is produced commercially from addition of water across the double bond in ethylene, and/or by fermentation of grains. It can be preferred that any alcohol used in the present invention contains less than five percent water, preferably less than approximately one percent water.
  • any alcohol used in the present invention contains less than five percent water, preferably less than approximately one percent water.
  • it is possible to keep a certain amount of water i.e., less than around 10%, ideally less than around 5%, more ideally, less than around 2%, and most ideally, less than around 1%) in the composition without resulting in product separation, because water is soluble in the alcohol blend.
  • the water, at these levels is not believed to result in substantially decreased performance, and, in some embodiments, may actually increase performance and/or reduce certain emissions.
  • the alcohol blends include at least 15%, more ideally, at least 20%, still more ideally, at least 25%, and even more ideally, more than 30% by volume of secondary and/or tertiary butanol. Ideally, the alcohol blends include at least 15%, more ideally, at least 20%, still more ideally, at least 25%, and even more ideally, more than 30% by volume of isopropanol.
  • the alcohols can be derived from a variety of sources.
  • the alcohols are derived in a two step process, where the first step is Fischer-Tropsch synthesis to produce a mainly olefmic fraction rich in C2-4 olefins, and the second step is hydrolysis of the C2-4 olefins to form C2-4 alcohols.
  • the C2-4 olefins can be, but need not be, isolated before the olefin hydrolysis. When they are isolated, they can be co-isolated with the C 2 - 4 paraffins (i.e., separating the C2-4 fraction from any methane/unreacted syngas/carbon dioxide, water, and C5 + fractions.
  • this raw material comprises biomass, such as corn stover, bagasse, switchgrass, algae, wood, sawdust, or waste streams derived from biomass, including the crude glycerol from biodiesel synthesis and hemicellulose, lignin or black liquor derived from cellulose and/or paper production.
  • biomass and waste streams can be converted to useful fuel and other products, rather than being sent to a landfill or, in the case of black liquor, often dumped into water supplies.
  • the process can be compatible with cellulosic ethanol production.
  • cellulosic ethanol will require the separation of cellulose from lignin and, optionally, hemicellulose. Delignification generates black liquor, which can be converted to syngas, and, ultimately, to a C2-4 alcohol-containing feedstock.
  • the hemicellulose can be depolymerized and, often inefficiently, fermented to alcohol, or also used as a feedstock to produce the C2-4 alcohols described herein.
  • the cellulosic ethanol can then be combined with the C 2 - 4 alcohols described herein, if desired.
  • the process can be optimized to use pure biomass as a starting material, and the C2-4 alcohols produced have a higher energy per unit volume than ethanol, without generating around 40% carbon dioxide by weight of biomass (the amount produced by bacteria or yeast in consuming the biomass to generate ethanol), while using the lignin, cellulose, and hemicellulose to generate these alcohols, it may be desirable to avoid ethanol production via fermentation altogether in favor of the approach described herein.
  • any Ci_4 saturated hydrocarbons can be isolated (though these can be isolated earlier, if desired). All or part of any Cs_i 5 hydrocarbons that are produced can also be isolated and used, for example, in gasoline production. These products can be isolated, for example, by distillation.
  • Unreacted syngas can be burned on-site to provide energy to run the plant, recycled through the process to improve yields, or used to generate electricity, as desired.
  • the alcohols can be blended with gasoline in any desired ratio, provided the energy per unit volume meets or exceeds that of E85. Since E85 includes predominantly ethanol and gasoline, and the alcohols produced according to the methods described herein can have an average carbon number of 3 or more, the energy content of the alcoholic mixture should meet or exceed that of E85 even without the addition of any gasoline.
  • the ethanol is present in lower concentrations than that in E85, the hygroscopic nature of ethanol is of a lesser concern. That is, the higher the concentration of C3 + alcohols in the fuel composition, the more easy it is to ship and store the fuel composition. In some embodiments, it can be possible to ship the fuel composition in a conventional pipeline, and/or store the composition without the retrofitting required to store E85.
  • some or all of the ethanol, propanol and/or isopropyl alcohol, and n-butanol can be produced by fermentation.
  • some or all of the olefins that can be hydrogenated to form the alcohols can be derived from sources other than Fischer-Tropsch synthesis (i.e., they can be formed in hydrocracking reactors, isolated from crude oil distillation, and the like). That said, production of olefins via Fischer-Tropsch synthesis, and the production of alcohols from olefins via olefin hydrolysis, is a preferred way to prepare the alcohol blends described herein. These processes are described in more detail below.
  • Fischer-Tropsch synthesis to form relatively low molecular weight olefins is well known. A brief discussion of Fischer-Tropsch synthesis is provided below.
  • syncrude hydrocarbon products
  • Fischer-Tropsch synthesis Alternatively, low molecular weight olefins can be formed, which can be used directly in the glycerol ether synthesis.
  • One advantage of the process described herein is that, unlike Fischer-Tropsch wax, which uses none of the oxygen in the syngas, the C 2 - 4 alcohol-containing product stream includes oxygen atoms, thus improving the overall product yield.
  • Another advantage is that, unlike the known processes for producing fuel products by hydrocracking Fischer-Tropsch wax, the instant process does not require a hydrocracker, but rather, only a means for adding water across the double bond of the olefins produced during the Fischer-Tropsch synthesis. Thus, with higher product yields and lower capitalization costs, the process offers benefits over traditional Fischer-Tropsch synthesis.
  • Fischer-Tropsch chemistry tends to provide a wide range of products, from methane and other light hydrocarbons, to heavy wax.
  • Syntroleum (a term used to define hydrocarbons in the diesel range formed by Fischer-Tropsch synthesis) is typically formed from the wax/heavy fraction obtained during Fischer-Tropsch Synthesis using a cobalt catalyst, or other catalyst with high chain growth probabilities, followed by hydrocracking of the wax.
  • Low molecular weight olefins are typically obtained from the light gas/naphtha heavy fraction obtained via Fischer-Tropsch chemistry using iron catalysts, or other catalysts with low chain growth probabilities. Because the desired alcohols are predominantly in the C2-4 range, production of C 2 - 4 olefins is more desired than production of Fischer-Tropsch wax. Therefore, catalysts with low chain growth probabilities are preferred.
  • Syngas is converted to liquid hydrocarbons by contact with a Fischer-Tropsch catalyst under reactive conditions.
  • a Fischer-Tropsch catalyst it may be desirable to purify the syngas prior to the Fischer-Tropsch reactor to remove carbon dioxide produced during the syngas reaction, and any sulfur compounds, if they have not already been removed. This can be accomplished by contacting the syngas with a mildly alkaline solution (e.g., aqueous potassium carbonate) in a packed column. This process can also be used to remove carbon dioxide from the product stream.
  • Fischer- Tropsch catalysts contain a Group VIII transition metal on a metal oxide support.
  • the catalyst may also contain a noble metal promoter(s) and/or crystalline molecular sieves.
  • the two transition metals that are most commonly used in commercial Fischer-Tropsch processes are cobalt or iron.
  • Ruthenium is also an effective Fischer-Tropsch catalyst but is more expensive than cobalt or iron.
  • platinum and palladium are generally preferred.
  • Suitable metal oxide supports or matrices which can be used include alumina, titania, silica, magnesium oxide, silica-alumina, and the like, and mixtures thereof.
  • Fischer-Tropsch processes produce a hydrocarbon product having a wide range of molecular sizes
  • the selectivity of the process toward a given molecular size range as the primary product can be controlled to some extent by the particular catalyst used.
  • the Fischer-Tropsch reaction is typically conducted at temperatures between about 300° F and 700° F (149° C to 371° C), preferably, between about 400° F and 550° F (204° C to 228° C).
  • the pressures are typically between about 10 and 500 psia (0.7 to 34 bars), preferably between about 30 and 300 psia (2 to 21 bars).
  • the catalyst space velocities are typically between about from 100 and 10,000 cc/g/hr., preferably between about 300 and 3,000 cc/g/hr.
  • the reaction can be conducted in a variety of reactors for example, fixed bed reactors containing one or more catalyst beds, slurry reactors, fluidized bed reactors, or a combination of different type reactors. Fischer-Tropsch processes which employ particulate fluidized beds in slurry bubble column reactors are described in, for example, U.S. Pat. Nos. 5,348,982; 5,157,054; 5,252,613; 5,866,621; 5,811,468; and 5,382,748, the contents of which are hereby incorporated by reference.
  • Low molecular weight fractions can be obtained using conditions in which chain growth probabilities are relatively low to moderate, and the product of the reaction includes a relatively high proportion of low molecular weight (C 2-8 ) olefins and a relatively low proportion of high molecular weight (C 30+ ) waxes.
  • Optimized conditions for producing predominantly C2-4 olefins are known to those of skill in the art. For example, conditions using an ammonia/iron catalyst are described, for tropsch.org/primary documcnts/prcscntations/rcccnt rcscarch/reccnt rcport.htm, the contents of which are hereby incorporated by reference, and which are described in detail below.
  • Synthesis gas with an H 2 ICO ratio of 2:1, containing 5 percent inert constituents and not more than 0. Ig total sulfur per 100 m 3 as raw material, can be used to maintain carbon monoxide conversion of about 95 per cent.
  • Increasing the pressure from 10 to 20 and from 20 to 25 arm can have a marked beneficial effect, as indicated by the reduction in temperature required to maintain conversion at a fixed space velocity and by the increase in space velocity permissible at fixed temperature without fall in conversion.
  • the CO conversion can be maintained at about 95 per cent at space velocities up to 1,000 vol. per vol. catalyst per hour.
  • the average velocity over duration of the experiment (128 days of synthesis) was approximately 500 per hour, and the average CO conversion, 95 per cent.
  • the reaction pressures can range from 10-25 atms. gauge, and the temperature can range from between about 208 and about 318°C, ideally between about 260 and about 300 0 C.
  • the H 2 : CO ratio in the synthesis gas can ideally range from about 2.03 : 1 to about 2.31 :1, and the synthesis gas space velocity, vol./vol. catalyst/hr, can range from about 366 to about 1050.
  • the recycle ratio, vol. residual gas vol. syn. gas can range from about 1.33 to about 7.1.
  • the CO conversion, as a weight percent, can range from about 78.1 to about 99.5, with most results being around 90% or more.
  • the percent conversion of CO to CO 2 can range from nil to about 29 percent, though it is typically less than around 6%.
  • the percentage of CO converted to CH 4 can range from about 10-28%, though is typically less than about 11-15%.
  • the percentage CO converted to higher hydrocarbons, as a percent of total, is typically in the range of from about 70 to about 80%.
  • a fixed bed reactor may convert about 95% of the carbon monoxide to products, whereas a fluidized bed may convert around 99+ percent of the carbon monoxide.
  • Methane can be produced in lower quantities in a fixed bed, relative to a fluidized bed.
  • Both fixed and fluidized bed reactors tend to produce around 77 to around 80% higher hydrocarbons, of which around 56 and around 75% by weight are C 2 _ 4 hydrocarbons, respectively.
  • the fractions in the 30-200 0 C boiling point range are around 34 and 18%, and in the 200-300 0 C boiling point range are around 6 and 4.5%, respectively.
  • At least some of the hydrocarbons in the C5-20 range can be used to produce gasoline, for example, by isomerizing and then hydrotreating/hydro finishing hydrocarbons in the Cs_io, ideally in the C 6 -S range. These hydrocarbons can then optionally be blended with the alcoholic blend and used in conventional gasoline or flexible fuel engines, as appropriate depending on the energy per unit volume. Assuming all of the hydrocarbons (LPG and hydrocarbons in the Cs_2o range) were used in fuel compositions, this would provide approximately 90% conversion of syngas to fuel compositions (LPG, alcohol blends that have the same or more energy per unit volume than E85, gasoline, jet, and diesel fuel), all without expensive hydrocracking.
  • the amount of products boiling below 200 0 C typically range from about 63 to about 76%, the amount of products boiling between 200 and 300 0 C typically ranged from about 13 to about 19%, and the amount of products boiling above 300 0 C typically range from about 10 to about 20%.
  • the olefin content of the fraction boiling below 200 typically ranges from about 65 to about 75%.
  • Those of skill in the art can also provide other suitable conditions for maximizing alcohol production directly from other catalysts.
  • molybdenum sulfide and other catalysts have been proposed for use in preparing higher alcohols, although with extremely poor syngas conversion and low catalyst lifetimes. While this can advantageously provide alternative fuel compositions, the alcohols are primary alcohols, not secondary or tertiary alcohols, and may not be preferred due to their potential to oxidize and form corrosive and odiferous carboxylic acids.
  • a fixed-bed reactor is used, and the catalyst is a commercial, fused-iron, synthetic-ammonia catalyst crushed and screened to 7/14 B. S. Test Sieves.
  • the catalyst can be reduced, for example, at 450 0 C, for a sufficient period of time, for example, for 24 hours, in a hydrogen atmosphere, ideally using pure hydrogen, at a space velocity of around 2,000 per hour.
  • the pressure, recirculation of residual gas, reaction temperature, and synthesis gas space velocity all have an affect on the product yield and distribution.
  • the temperature and other factors are adjusted to maintain a constant carbon monoxide conversion of greater than about 85%, ideally, greater than about 95 per cent.
  • the exact values for these factors will be expected to vary depending on the nature of the reactor, that is, the reactor size, cooling conditions, type of catalyst, and the like. Those of skill in the art will readily understand how to optimize the reaction conditions to achieve a desired product distribution. At least one author has observed that an increase in pressure from 10 to 20 and from
  • the same Fischer-Tropsch catalysts can be used in fixed and fluidized beds.
  • the synthesis gas used can be of a similar composition to that use in a fixed-bed, however, to minimize wax and carbon formation, the H 2 :CO ratio can be increased (i.e., to around 2.35:1). It may be desirable to use relatively high recycle ratios in order to maintain the catalyst in a fluid condition without using excessively high synthesis-gas rates.
  • the catalyst is more active in the fluidized powder form than in the fixed bed. It is also believed that by using a high recycle ratio, one can eliminate or reduce carbon dioxide formation, and increase H 2 /CO utilization. One can obtain a higher proportion of C 2 -C 4 hydrocarbons in a fluidized bed relative to a fixed bed.
  • a synthetic ammonia iron catalyst When a synthetic ammonia iron catalyst is used at relatively high temperatures (280° to 330 0 C), the alcohol content of the products is low, but the olefin content very high.
  • the olefins can be hydrogenated using an acid catalyst, forming iso-alcohols rather than normal alcohols.
  • the olefins are a mixture of olefins, in unpurified form, obtained by the cracking of crude oil, and in another embodiment, from Fischer-Tropsch synthesis. Since mixtures of alcohols are the desired end product, it is unnecessary to use pure olefins.
  • Any acid catalyst that is suitable for performing etherif ⁇ cations can be used, in any effective amount and any effective concentration.
  • suitable acids include, but are not limited to, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and solid catalysts such as Dowex 50TM. Strong acids are preferred catalysts. The most preferred acid catalyst is sulfuric acid.
  • Olefin hydration using zeolite catalysts is known.
  • lower olefins in particular, propylene, are catalytically hydrated over a crystalline aluminosilicate zeolite catalyst having a silica to alumina ratio of at least 12 and a Constraint Index of from 1 to 12, e.g., HZSM-5 type zeolite, to provide the corresponding alcohol, essentially free of ether and hydrocarbon by-product.
  • U.S. Patent No. 4,499,313 discloses hydrating an olefin to the corresponding alcohol in the presence of hydrogen-type mordenite or hydrogen-type zeolite Y, each having a silica-alumina molar ratio of 20 to 500.
  • the use of such a catalyst is said to result in higher yields of alcohol than olefin hydration processes which employ conventional solid acid catalysts.
  • Use of the catalyst is also said to offer the advantage over ion-exchange type olefin hydration catalysts of not being restricted by the hydration temperature.
  • Reaction conditions employed in the process include a temperature of from 50-300 0 C, preferably 100-250 0 C, a pressure of 5 to 200 kg/cm 2 to maintain liquid phase or gas-liquid multi-phase conditions and a mole ratio of water to olefin of from 1 to 20.
  • the reaction time can be 20 minutes to 20 hours when operating batchwise and the liquid hourly space velocity (LHSV) is usually 0.1 to 10 in the case of continuous operation.
  • LHSV liquid hourly space velocity
  • European Patent Application 210,793 describes an olefin hydration process employing a medium pore zeolite as hydration catalyst. Specific catalysts mentioned are Theta-1, said to be preferred, ferrierite, ZSM-22, ZSM-23 and NU-10.
  • N-butanol has approximately the same energy per unit volume as gasoline, but is prone to oxidation to form butyric acid.
  • hydrolysis of 1-butene or 2-butenes produces secondary and/or tertiary butanol, not n-butanol.
  • the oxidation product of sec- butanol is methylethyl ketone, and t-butanol is not very prone to oxidation (except when combusted). Therefore, at least one problem associated with the use of butanol (i.e., the oxidation to butyric acid and the resulting unpleasant odor) is not present with the fuel compositions described herein.
  • all or part of the C2-4 paraffins may be dehydrogenated to mono-olefms, and hydro lyzed to form additional alcohols. All or part of the hydrogen thus produced can be recycled into the process, for example, to increase the hydrogen/carbon monoxide ratio in the syngas.
  • a well known dehydrogenation process is the UOP PacolTM process. Syntroleum has demonstrated the feasibility of dehydrogenation of paraffins to mono-olef ⁇ ns. Thus, suitable dehydrogenation processes are well known and need not be described in more detail herein.
  • Alpha and internal-olefms can be hydroformulated in a process commonly known as the "OXO" process.
  • OXO organic compound
  • the OXO process to make alcohols is described in detail in Kirk- Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 1, pp. 903 8 (1991), the contents of which are hereby incorporated by reference.
  • the first step generally follows the following equation:
  • the hydroformulation product can then be hydrogenated to form alcohols either in the step illustrated above, or in a second step, illustrated by the equation below:
  • R-CH 2 -CH 2 - CH 0+H 2 — -> R-CH 2 -CH 2 -CH-OH
  • the OXO process is characterized mainly by a certain ratio of normal product to isomeric product and the pressure of the reaction.
  • a conventional OXO process employs a Co-hydrocarbonyl catalyst at pressures from about 3000 psig to about 5000 psig, temperatures from about HO to about 180 0 C, and a ratio of CO :H2 of about 1 :1.
  • the OXO process is a two-step process, wherein first the aldehyde is formed and separated, and second the aldehyde is hydrogenated to alcohols or oxidized to acids.
  • a process employed by Shell functions at around 400 psig and uses a cobalt catalyst liganded with a tributyl phosphine instead of one of the carbonyl ligands. This process typically requires a ratio of CO:H 2 of around 1 :2, and generates an alcohol product in a single step.
  • OXO process converts alpha-olefms much more readily than internal olefins and occurs in an isomerizing atmosphere. Thus, even internal olefins are partially converted into linear alcohols.
  • the Shell process converts 75% of feed internal olefins to primary alcohols, while Davy process reportedly converts even more.
  • a synthesis gas without diluents is used, a synthesis gas from the Syntroleum ATR containing from about 10 to about 60% N 2 can be used. Because hydro formulation adds a --COH group to an olefin, the lightest of the produced alcohols will boil higher than the heaviest of the contained olefins, thus making the separation relatively facile.
  • a predominantly C 3 _ 5 alcohol stream such as a composition including between about 60 and about 90%, or consisting essentially of, C3-5 alcohols, can be obtained. Because this product will have a C4 average molecular weight, it will have energy per unit volume approximately equal to that of gasoline, and can run in a conventional gasoline engine without the need for modification (i.e., no need for a flexible fuel engine). This is advantageous over hydro formylation of higher olefins, since it produces a fuel product that can run in a conventional engine, and the boiling points of the alcohols are not too high for such use.
  • the alcohol blends can be used as described herein.
  • the alcohol-containing compositions described herein can be blended with gasoline to increase the energy per unit volume.
  • the amount of alcohol that can be present in the gasoline/alcohol blends can vary.
  • the alcohols can be the only components present in the fuel composition, along with the optional presence of conventional fuel additives.
  • the ratio of gasoline to the alcohol composition can range from 1 : 99 to 99: 1 by volume, although it can be preferred that the amount of gasoline present is less than around 15% by volume because the energy content will meet or exceed that of E85. That said, given the size of the gasoline market, it may be desirable to use as little as 1-10% of the alcohol composition in gasoline/alcohol blends.
  • the amount of the alcohol composition is between about 1 and 20 percent by volume, and more ideally, about 15 to 20 percent by volume.
  • the amount of alcohol composition is between about 75 and 85 percent by volume, and more ideally, about 15 to 20 percent by volume.
  • the alternative fuel composition described herein can be prepared by mixing gasoline with the alcohol blends described herein, in any suitable manner, and in any desired ratio.
  • the gasoline is present in a range of about 75 to 85 percent, with between about 5 and about 20 percent of the alcohol blends described herein, each by volume, with the balance being other additives as described above.
  • a fuel composition such as a gasoline/alcohol composition
  • at least a portion of the ethanol and/or butanol are derived from renewable resources.
  • the fuel composition can be formed by mixing/blending the gasoline and the alcohols. Means for mixing these components are well known to those of skill in the art. During blending, it can be advantageous to remove aliquots of the fuel composition and measure various properties, such as vapor pressure and energy content, to ensure that the mixture/blend has the desired properties.
  • the resulting fuel compositions and/or blends can be used at least in flexible fuel vehicles, and, ideally, in standard gasoline engines (depending on how much gasoline is present).
  • the fuel compositions can optionally, but preferably, include one or more additives, such as lubricants, emulsif ⁇ ers, wetting agents, densif ⁇ ers, fluid-loss additives, corrosion inhibitors, oxidation inhibitors, friction modifiers, demulsif ⁇ ers, anti-wear agents, anti- foaming agents, detergents, rust inhibitors and the like.
  • additives such as lubricants, emulsif ⁇ ers, wetting agents, densif ⁇ ers, fluid-loss additives, corrosion inhibitors, oxidation inhibitors, friction modifiers, demulsif ⁇ ers, anti-wear agents, anti- foaming agents, detergents, rust inhibitors and the like.
  • additives such as lubricants, emulsif ⁇ ers, wetting agents, densif ⁇ ers, fluid-loss additives, corrosion inhibitors, oxidation inhibitors, friction modifiers, demulsif ⁇ ers, anti-wear agents, anti- foaming agents, detergents, rust inhibitors and the like.
  • 5,189,012 the contents of which are hereby incorporated by reference, can be blended with the fuel, provided that the final blend has the necessary octanelcetane values, pour, cloud and freeze points, kinematic viscosity, flash point, and toxicity properties.
  • the total amount of additives is preferably between 50-100 ppm by weight for 4-stroke engine fuel, and for 2-stroke engine fuel, additional lubricant oil may be added.
  • Engine performance additives can be added to improve engine performance.
  • Fuel and/or crankcase lubricant can form deposits in the nozzle area of injectors—the area exposed to high cylinder temperatures.
  • Injector cleanliness additives can be added to minimize these problems.
  • Ashless polymeric detergent additives can be added to clean up fuel injector deposits and/or keep injectors clean.
  • These additives include a polar group that bonds to deposits and deposit precursors and a non-polar group that dissolves in the fuel.
  • Detergent additives are typically used in the concentration range of 50 ppm to 300 ppm.
  • detergents and metal rust inhibitors include the metal salts of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkyl salicylates, naphthenates and other oil soluble mono and dicarboxylic acids such as tetrapropyl succinic anhydride.
  • Neutral or highly basic metal salts such as highly basic alkaline earth metal sulfonates (especially calcium and magnesium salts) are frequently used as such detergents.
  • nonylphenol sulfide Similar materials made by reacting an alkylphenol with commercial sulfur dichlorides. Suitable alkylphenol sulfides can also be prepared by reacting alkylphenols with elemental sulfur.
  • Lubricity additives can also be added. Lubricity additives are typically fatty acids and/or fatty esters. Examples of suitable lubricants include polyol esters of C12-28 acids. The fatty acids are typically used in the concentration range of 10 ppm to 50 ppm, and the esters are typically used in the range of 50 ppm to 250 ppm.
  • organometallic compounds for example, barium organometallics, act as combustion catalysts, and can be used as smoke suppressants.
  • Adding these compounds to fuel can reduce the black smoke emissions that result from incomplete combustion.
  • Smoke suppressants based on other metals e.g., iron, cerium, or platinum, can also be used.
  • Anti-foaming additives such as organosilicone compounds can be used, typically at concentrations of 10 ppm or less. Examples of anti-foaming agents include polysiloxanes such as silicone oil and polydimethyl siloxane; acrylate polymers are also suitable.
  • Drag reducing additives can also be added to increase the volume of the product that can be delivered. Drag reducing additives are typically used in concentrations below 15 ppm.
  • Antioxidants can be added to the distillate fuel to neutralize or minimize degradation chemistry. Suitable antioxidants include, for example, hindered phenols and certain amines, such as phenylenediamine. They are typically used in the concentration range of 10 ppm to 80 ppm. Examples of antioxidants include those described in U.S. Pat. No. 5,200,101, the contents of which are hereby incorporated by reference. The '101 patent discloses certain amine/hindered phenol, acid anhydride and thiol ester-derived products.
  • Acid-base reactions are another mode of fuel instability.
  • Stabilizers such as strongly basic amines can be added, typically in the concentration range of 50 ppm to 150 ppm, to counteract these effects.
  • Metal deactivators can be used to tie up (chelate) various metal impurities, neutralizing their catalytic effects on fuel performance. They are typically used in the concentration range of 1 ppm to 15 ppm.
  • Multi-component fuel stabilizer packages may contain a dispersant.
  • Dispersants are typically used in the concentration range of 15 ppm to 100 ppm.
  • Biocides can be used when contamination by microorganisms reaches problem levels. Preferred biocides dissolve in both the fuel and water and can attack the microbes in both phases. Biocides are typically used in the concentration range of 200 ppm to 600 ppm.
  • Demulsif ⁇ ers are surfactants that break up emulsions and allow fuel and water phases to separate. Demulsif ⁇ ers typically are used in the concentration range of 5 ppm to 30 ppm.
  • Dispersants are well known in the lubricating oil field and include high molecular weight alkyl succinimides being the reaction products of oil soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof.
  • Corrosion inhibitors are compounds that attach to metal surfaces and form a barrier that prevents attack by corrosive agents. They typically are used in the concentration range of 5 ppm to 15 ppm. Examples of suitable corrosion inhibitors include phosphosulfurized hydrocarbons and the products obtained by reacting a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide.
  • oxidation inhibitors include antioxidants such as alkaline earth metal salts of alkylphenol thioesters having preferably Cs_i 2 alkyl side chain such as calcium nonylphenol sulfide, barium t-octylphenol sulfide, dioctylphenylamine as well as sulfurized or phosphosulfurized hydrocarbons.
  • antioxidants such as alkaline earth metal salts of alkylphenol thioesters having preferably Cs_i 2 alkyl side chain such as calcium nonylphenol sulfide, barium t-octylphenol sulfide, dioctylphenylamine as well as sulfurized or phosphosulfurized hydrocarbons.
  • Additional examples include oil soluble antioxidant copper compounds such as copper salts Of C 10-18 oil soluble fatty acids.
  • friction modifiers examples include fatty acid esters and amides, glycerol esters of dimerized fatty acids and succinate esters or metal salts thereof.
  • Pour point depressants such as C 8-18 dialkyl fumarate vinyl acetate copolymers, polymethacrylates and wax naphthalene are well known to those of skill in the art.
  • anti-wear agents examples include zinc dialkyldithiophosphate, zinc diary diphosphate, and sulfurized isobutylene. Additional additives are described in U.S. Pat. No.5, 898, 023 to Francisco, et al., the contents of which are hereby incorporated by reference.
  • the C2-4 alcohols can be used to fuel flexible fuel vehicles, alone or in combination with gasoline and/or gasoline additives as described herein, or in conventional gasoline engines when combined with gasoline at a ratio of about 5-25% of the fuel additives to 75- 95% of the C 2 - 4 alcohols.
  • the C 2 - 4 alcohols can also be used to fuel solid oxide fuel cells, and produce significantly more electrical energy, per volume of alcohol feedstock, than methanol or ethanol.
  • solid oxide fuel cells and other fuel cells typically require fuel sources that are soluble in water, and above four carbons, alcohols tend not to be very soluble in water, so the C2-4 alcohol product provides about as much energy per unit volume as possible to these fuel cells.
  • the higher molecular weight hydrocarbons are typically a combination of olefins and paraffins. They can be isomerized, cyclized, dimerized or hydrotreated as desired to yield fuel in the gasoline, jet and/or diesel range.
  • the C2-4 hydrocarbons can be used for any use conventional LPG is used, including powering certain alternative fuel vehicles, for example, taxis and buses, heating houses, and as a fuel for barbecues. Any methane that is formed can be recycled through the syngas generator, or used for any conventional use for methane, including heating homes and producing methanol.
  • the water from the Fischer- Trospch step may include alcohols and other oxygenated products, which can be isolated and combined with the remainder of the alcohol products, or the water can be passed through a fuel cell to generate electricity.

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Abstract

L'invention concerne des compositions de substitution de carburant, des mélanges des compositions de carburant de substitution et de l'essence et leurs procédés de préparation et d'utilisation. Les compositions de carburant de substitution renferment en théorie de l'éthanol, de l'alcool isopropylique et au moins un du sec-butanol ou du t-butanol, et renferment théoriquement une proportion n'excédant pas 3% de méthanol et 15% de C5 ou des alcools supérieurs. Les compositions de carburant peuvent être préparées par synthèse de Fischer-Tropsch afin de convertir le gaz de synthèse en un flux de produit comprenant des C2-4 oléfines et d'hydrolyser ces oléfines. Ce procédé facilite l'isolation des C2-4 alcanes car la différence du point d'ébullition de ces alcanes est sensiblement inférieure à celle des C2-4 alcools. En théorie, la composition produit plus d'énergie par volume unitaire que E85, même sans adjonction d'essence, bien que les compositions puissent être mélangées avec de l'essence quelle que soit la proportion voulue. Le carburant de substitution résultant peut être dérivé, du moins partiellement, de ressources renouvelables, et une proportion importante de la molécule est dérivée de l'eau utilisée pour hydrolyser les oléfines. Les compositions de carburant de substitution, et leur mélange avec de l'essence peuvent contribuer à réduire la dépendance des USA du pétrole étranger.
EP07762313A 2007-03-21 2007-05-24 Production d'un mélange d'alcool utilisable dans des véhicules flexibles en carburant via la synthèse de fischer-tropsch Withdrawn EP2121878A4 (fr)

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US20100005709A1 (en) 2010-01-14

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