CA2633446A1 - Process for converting carbohydrates to hydrocarbons - Google Patents

Process for converting carbohydrates to hydrocarbons Download PDF

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Publication number
CA2633446A1
CA2633446A1 CA002633446A CA2633446A CA2633446A1 CA 2633446 A1 CA2633446 A1 CA 2633446A1 CA 002633446 A CA002633446 A CA 002633446A CA 2633446 A CA2633446 A CA 2633446A CA 2633446 A1 CA2633446 A1 CA 2633446A1
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Prior art keywords
carbohydrate
range
zsm
mixture
zeolite
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CA002633446A
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French (fr)
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CA2633446C (en
Inventor
Jianhua Yao
Edward L. Sughrue
James B. Kimble
Joseph B. Cross
Marvin M. Johnson
Dhananjay B. Ghonasgi
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Phillips 66 Co
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

Processes for the conversion of carbohydrates to gasoline boiling range hydrocarbons, and processes for increasing the solubility of carbohydrates used in such processes are disclosed. The solubility of carbohydrates may be increased by contacting the carbohydrate with an ion-exchange resin. The dissolved product may be hydrogenated and reacted in the present of a catalyst to form a reaction product containing non-aromatic and aromatic gasoline boiling range hydrocarbons.

Description

PROCESS FOR CONVERTING CARBOHYllRATES TO HYDROCARBONS
FIELD OF THE INVENTION

The present invention relates generally to the conversion of carbohydrates to fuel range hydrocarbons.

BACKGROUND OF THE INVENTION

There is a national interest in the discovery of alternative sources of fuels and chemicals, other than from petroleum resources. As the public discussion concerning the availability of petroleum resources and the need for alternative sources continues, it is anticipated that future government mandates will require transportation fuels to include, at least in part, hydrocarbons derived from sources besides petroleum. As such, there is a need to develop alternative sources for hydrocarbons useful for producing fuels and chemicals.
One possible alternative source of hydrocarbons for producing fuels and chemicals is the natural carbon found in plants and animals, such as for example, in the form of carbohydrates. These so-called "natural" carbon resources (or renewable ] 5 hydrocarbons) are widely available, and remain a target alternative source for the production of hydrocarbons. For example, it is known that carbohydrates and other sugar-based feedstocks can be used to produce ethanol, which has been used in gasohol.and other energy applications. However, the use of ethanol in transportation fuels has not proven to be cost effective.

Carbohydrates, however, also can be used to produce fuel range hydrocarbons. The 'upgrading of biologically derived materials to materials useful in producing fuels is known in the art. However, many carbohydrates (e.g., starch) are undesirable as feed stocks due to the costs associated with converting them to a usable form.
In addition, many carbohydrates are known to be "difficult" to convert due to their chemical structure, or that the hydrocarbon product produced is undesirable or will result in low quantities of desirable product. Among the compounds that are stated to be difficult to convert include compounds with low effective hydrogen to carbon ratios, including carbohydrates such as starches and sugars, carboxylic acids and anhydrides, lower glycols, glycerin and other polyols and short chain aldehydes. As such, efforts have been made to convert traditionally difficult to convert materials to hydrocarbons by focusing on methods for increasing the effective hydrogen to carbon ratio of the reactants, including converting oxygenates in the presence of hydrogen, CO, steam, nitrogen, or other reactants, and by employing various catalysts. However, these processes are often complex and are costly, and the reaction products produced as a result of these processes are oftentimes undesirable, or result in low weight percentages, and often result in an increase in undesirable byproducts such as the production of carbon monoxide and carbon dioxide.

In addition, many carbohydrates (such as complex polysaccharides, including corn starch) in their raw form are undesirable as feeds. For example, starch, in its native form, is a solid and as such, prior to use, it is desirable to convert the solid form into a liquid forn-i for ease of processing. However, when starch is combined with liquid, it becomes extremely viscous, making dissolution difficult. As a result, many processes employed only result in the partial hydrolyzation of the carbohydrate starting material, which necessitates addressing the undissolved solid fraction in the reaction zone. In addition, because of the viscosity, it is often required to mix the carbohydrate with large volumes of water and/or chemicals, along with harsh reaction conditions in order to achieve the desired dissolution.

As such, development of a process for increasing the solubility of carbohydrates in the conversion of carbohydrates to hydrocarbons would be a significant contribution to the art. In addition, development of a process for converting carbohydrates to hydrocarbons which yields significant quantities of desirable hydrocarbon products such as aromatics and olefins would be a significant contribution to the art.
Furthermore, development of a carbohydrate conversion process resulting in a product with reduced byproducts such as carbon monoxide and carbon dioxide, and coke production, would be a significant contribution to the art.

SUMMARY OF THE INVENTION

Accordingly, it is one aspect of the present invention to provide a process for increasing the solubility of a carbohydrate, such as for example starch, utilizing ion-exchange resins, for use in a process for the conversion of the carbohydrate to gasoline boiling range hydrocarbons, such 'as for example non-aromatic and aromatic boiling range hydrocarbons.
A further aspect of the present invention is to provide an improved process for the conversion of carbohydrates to hydrocarbons, particularly non-aromatic and aromatic gasoline boiling range hydrocarbons, using an improved integrated process which produces an improved yield of reaction products including aromatic gasoline boiling range hydrocarbons, such as for example C6-C8 aromatic hydrocarbons (benzene, toluene, xylene, and ethyl benzene).

A further aspect of the present invention is to provide a process for converting carbohydrate-containing compounds, including starch, corn syrup, and lactic acid, to non-aromatic and aromatic gasoline boiling range hydrocarbons.

A further aspect of the present invention is to provide a process for the conversion of carbohydrates to hydrocarbons in which the rate of coke forination and the production of CO,, by-products during such conversion is minimized.

In one embodiment of the present invention, a process is provided for increasing the solubility of a carbohydrate-containing compound, such as a polysaccharide, for example, corn starch, by contacting the carbohydrate-containing compound with an ion-exchange resin in a liquid medium to form a mixture. The mixture is then heated at a temperature sufficient to substantially dissolve the mixture in the liquid medium. The dissolved mixture (i.e., substantially or completely dissolved mixture) may then be used in other inventive processes of the present invention, including processes for the conversion of carbohydrates to hydrocarbons, particularly non-aromatic and aromatic gasoline boiling range hydrocarbons.

In another embodiment of the present invention, a process is provided for converting carbohydrates to hydrocarbons which includes contacting a polysaccharide with an ion-exchange resin in a liquid medium under a condition to substantially dissolve the polysaccharide in the liquid medium to form a mixture. The mixture (i.e., substantially or completely dissolved mixture) is then contacted with a hydrogenation catalyst under a condition (i.e., reaction or conversion condition) sufficient to form a hydrogenated product.
The hydrogenated product may then be contacted with a catalyst composition under a condition (i.e., reaction or conversion condition) sufficient to form a reaction product containing gasoline boiling range hydrocarbons.
In another embodiment of the present invention, a process is provided for converting carbohydrates to hydrocarbons which includes contacting an aqueous solution containing at least one carbohydrate with a hydrogenation catalyst under a condition sufficient to form a hydrogenated product. The hydrogenated product may then be contacted with a catalyst composition under a condition (i.e., reaction or conversion condition) sufficient to form a reaction product containing gasoline boiling range hydrocarbons.

Other objects, advantages and embodiments of the invention will be apparent from the following detailed description of the invention and the appended claims.

When used herein, the terms "comprising" or "including" when introducing a list of alternatives means that additional elements to those listed may be present. The term "consists of' means that the feature that is stated to "consist of' the stated material must consist only of those elements.

When used herein the phrases "consists essentially of', "consisting essentially of' and similar phrases do not exclude the presence of other steps, elements, or materials that are not specifically mentioned in this specification, as long as such steps, elements or materials, do not affect the basic and novel characteristics of the invention, additionally, they do not exclude impurities normally associated with the elements and materials used.

DETAILED DESCRIPTION OF THE INVENTION

Carbohydrates, such as starches and sugars may be converted in accordance with the present invention to form a hydrocarbon mixture useful for liquid fuels and chemicals. The term, "carbohydrate" is used generally to refer to a compound of carbon, hydrogen and oxygen having the general formula Cx(HZO)y, in which the ratio of hydrogen to oxygen is the same as in water. Carbobydrates include monosaccharides, polysaccharides, and mixtures of monosaccharides and/or polysaccharides. The term "monosaccharide" or "monosaccharides" are generally hydroxy aldehydes or hydroxy ketones which cannot be hydrolyzed into any simpler carbohydrate. Examples of monosaccharides include dextrose, glucose, fructose and galactose. The term "polysaccharide" or "polysaccharides" include those saccharides containing more than one monosaccharide unit. This term also includes disaccharides (such as sucrose, maltose, cellobiose, and lactose) and oligosaccharides.

Generally, carbohydrates useful in the present invention are characterized as having an overall effective hydrogen to carbon ratio of about zero, although carbohydrates having an overall effective hydrogen to carbon ratio greater than zero may also be used.
The effective hydrogen to carbon ratio may be determined by the gross composition of the carbohydrate starting material according to the formula described in U.S. Pat.
No. 4,503,278 of (H/C)eff = (H-2(0) - 3N - N - 2S)/C

where H, C, 0, N, and S are the relative atom ratios of hydrogen, carbon, oxygen, nitrogen and sulfur as determined by elemental analysis on an anhydrous basis. For example, the approximate chemical formula for starch is (C6H10O5),,. Inserting the appropriate values in the above equation gives:

H/Cere= (10-2(5) - 3(0)-0-2(0))/10 = 0/10 = 0.

Useful carbohydrates in the present invention include, but are not limited to, carbohydrates that can be converted to hydrocarbons when contacted under suitable reaction conditions. The carbohydrate starting material may be insoluble in an aqueous medium such as water, substantially insoluble in an aqueous medium, or partially insoluble in an aqueous medium. In addition, carbohydrates useful in the present invention may be soluble in an aqueous medium, substantially soluble in an aqueous medium, or partially'soluble in an aqueous medium. In addition, carbohydrates useful in the present invention may be in a pure form, or may be mixed with other components, including but not limited to, additives.
Examples of carbohydrates useful as starting materials in accordance with the present invention include, but are not limited to, polysaccharides such as sucrose, maltose, lactose, cellobiose, melibiose raffininose, starch (e.g., corn starch or other starches derived from other cereal grains such as wheat and rice, or those from tubers, such as potato, tapioca, and arrowroot, or those that are waxy starches such as waxy moil, maize and rice) and starch decomposition products such as dextrin and corn syrup (also known as glucose syrup).

In one embodiment of the present invention, insoluble starch (e.g., cornstarch) is used as the starting material. Starch, in its native form, is insoluble in water.
Cornstarch may be found, for example, within corn kernels as a long polymer polysaccharide composed of two structural classes: amylose and amylopectin.
Amylose, which is about 25% of the cornstarch, is water soluble while ainylopectin, which is about 75% of the cornstarch, is insoluble.

In another embodiment of the present invention, corn syrup (sometimes referred to as glucose syrup) is used as the starting material. Corn syrup generally is a mixture of glucose, maltose, and maltodextrins and produced by the acid hydrolysis of starch. Generally, in the production of corn syrup, the starch source (e.g., corn) is suspended in water and liquefied in the presence of acid and/or enzymes that convert the starch first, to a mixture of glucose, maltose, and higher saccharides.
Throughout the process, the processor may halt the actions of the acid or enzyme to produce the proper mixture of sugars for syrups to meet different needs. The degree of conversion of the starch varies, with a consequent effect on the dextrose equivalent (D.E.) or reducing power of the syrup. Thus, corn syrups generally have a range of molecular compositions, rather than a specific molecular composition.

In one embodiment of the present invention, carbohydrates may optionally be first hydrolyzed in a liquid medium such as water. It is understood that carbohydrates may not need to be hydrolyzed, as the carbohydrate or carbohydrate-containing material may be in a suitable aqueous form for processing and for converting the carbohydrate to a hydrocarbon product. In one embodiment of the present invention, the solubility of a carbohydrate, such as for example a polysaccharide such as starch, in a liquid medium may be increased by contacting the carbohydrate with an ion-exchange resin under a condition sufficient to partially, substantially, or completely, dissolve the carbohydrate in the liquid medium. In another embodiment of the present invention, the solubility of the carbohydrate in a liquid medium may be increased by contacting a carbohydrate with an ion-exchange resin in a liquid medium to form a mixture, and heating the mixture at a temperature sufficient to partially, substantially, or completely dissolve the mixture in the liquid medium.

The amount of carbohydrate used as the starting material in the present invention will vary depending on the size of the commercial process or suitability of the mixing/reaction vessel. Generally, when combined with water or other liquid at elevated temperatures, carbohydrates such as starch granules absorb water and swell to many times their original size thus making the gelatinized or swollen product very viscous. For example, when starch is used as a starting material in a solid form, the starch may contain in the range of from about 10 to about 90 % solid particle, in relation to the percentage of liquid medium. In one embodiment of the present invention, the carbohydrate/liquid medium ratio is the range of from about 10 to about 80 weight percent, based on the total weight of the carbohydrate/liquid medium mixture. In another embodiment of the present invention, the carbohydrate/liquid medium ratio is the range of from about 15 to about 70 weight percent, based on the total weight of the carbohydrate/liquid medium mixture. In another embodiment of the present invention, the carbohydrate/liquid medium ratio is the range of from about 20 to about 60 weight percent, based on the total weight of the carbohydrate/liquid medium mixture.

Ion-exchange resins useful in the present invention generally are insoluble matrices (or support structures) of electrolytes normally in the forrn of small (I-2mm diameter) beads, fabricated from an organic polymer substrate (such as polystyrene). In addition, the ion-exchange resins contain two types of ions, those which are bound within the subsrate, and the oppositely charged counter ions that are free. When an ion-exchange resin is immersed in a medium in which it is insoluble or partially or substantially insoluble, the counter ions are mobile and may be exchanged for other counter ions from the surrounding medium, whereas ions of the same type of charge as the bound ions do not have free movement into and out of the polymer substrate. Generally, ion exchange resins useful in the present invention may be classified based on the charge of the exchangeable counter ion (cation exchanger or anion exchanger) and the ionic strength of the bound ion (strong exchanger or weak exchanger). Ion-exchange resins useful in the present invention may include by way of example strong cation-exchange resins or strongly acidic cation-exchange resins such as those containing sulfonic acid groups or corresponding salts.
In addition, ion-exchange resins useful in the present invention may include by way of example weak cation-exchange resins or weakly acidic cation-exchange resins, such as those containing carboxylic acid groups or corresponding salts. In addition, ion exchange resins useful in the present invention may contain or be supported on various polymer substrates including, but not limited to, styrene, polystyrene, and acrylic-based monomers.

Non-limiting suitable examples of ion-exchange resins useful in the present invention, include but are not limited to, AmberlystTM-15, AmberlystTM XN-1005, AmberlystTM XN-1008, AmberlystTM XN-1010, AmberlystTM XN-1011, AmberliteTM
200, AmberliteTM-IR-120 (H), and combinations thereof. In one embodiment of the present invention, the ion-exchange resin is a polystyrene supported resin containing sulfonic acid groups commercially available from Rohm and Haas under the trade designation "AmberliteTM IR-120 (H)."

Generally, ion exchange resins useful in the present invention are present in an amount in the range of from about .02 to about 10 percent, based on the weight of the carbohydrate/liquid medium mixture. In one embodiment of the present invention, the ion exchange resin is present in an amount in the range of from about .04 to about 4 percent, based on the weight of the carbohydrate/liquid medium mixture. In another embodiment of the present invention, the ion exchange resin is present in an amount in the range of from about .06 to about 2 percent, based on the weight of the carbohydrate/liquid medium mixture. In another embodiment of the present invention, the ion exchange resin is present in an amount in the range of from about .08 to about 1 percent, based on the weight of the carbohydrate/liquid medium mixture.

Carbohydrates useful in the present invention may be dissolved in any aqueous reaction medium, including water. In addition reaction of carbohydrates with ion-exchange resins in accordance with the present invention may be carried out in any suitable type of apparatus which enable intimate contact of the reactants and control of the operating conditions. The process may be carried out in batch, semi-continuous, or continuous operation. In one embodiment of the present invention, a batch operation in a conventional autoclave is used.

In one embodiment of the present invention, the carbohydrate/liquid medium/ion- exchange resin mixture may be loaded in a sufficient amount in an autoclave and the system flushed with nitrogen or other suitable gas and sealed. In one embodiment of the present invention, the mixture may be contacted under a condition sufficient to produce a partially dissolved mixture, substantially dissolved mixture, or completely dissolved mixture. Generally, such a condition may include heating the mixture for a time period in the range of from about 10 minutes to about 50 minutes at a temperature in the range of from about 80 C to about 300 C, and a pressure in, the range of from about 10 to about 100 psig. It is, however, understood that higher and lower temperatures and pressures than those described above may be used when deemed necessary or desirable to optimize results.

In one embodiment of the present invention, the carbohydrate/liquid medium/ion- exchange resin mixture is heated at a temperature is in the range of from about 50 C to about 250 C. In another embodiment of the present invention, the temperature is in the range of from about 100 C to about 200 C. In another embodiment of the present invention, the temperature is in the range of from about 110 C to about 150 C.
In another embodiment of the present invention, the carbohydrate/liquid medium/ion exchange resin mixture is subjected to a pressure is in the range of from about 0 to about 500 psig. In another embodiment of the present invention, the pressure is in the range of from about 10 to about 250 psig. In another embodiment of the present invention, the pressure is in the range of from about 15 to about 100 psig. In one embodiment of the present invention, the carbohydrate/liquid medium/ion-exchange resin mixture is subjected to a temperature and pressure for a time period in the range of from about 10 minutes to about 120 minutes. .In another embodiment of the present invention, the time period is in the range of from about minutes to about 90 minutes. In still another embodiment of the present invention, the time period is in the range of from about 25 minutes to about 60 minutes.

In one embodiment of the present invention, the carbohydrate/liquid medium/ion exchange resin mixture is heated to a temperature of approximately 140 C and 20 held for 30 minutes. In one embodiment of the present invention, the carbohydrate/liquid medium/ion exchange resin mixture is not subjected to additional pressure, other than the natural pressure resulting from heating that carbohydrate/liquid medium/ion exchange resin mixture.

Generally, the carbohydrate-containing starting material, after being contacted with a suitable ion-exchange resin under a sufficient condition, produces a partially dissolved, substantially dissolved, or completely dissolved, carbohydrate starting material in the liquid medium. In one embodiment of the present invention, 100% of the carbohydrate is dissolved in the aqueous medium. In another embodiment of the present invention, greater than 95 percent of the carbohydrate is dissolved in the aqueous medium.
In addition, approximately 50-80% of the carbohydrate starting material (for example, polysaccharides) may be converted to its basic monosaccharide, as a result of the hydrolysis in the present of an ion-exchange resin, as measured by dextrose equivalents tests.
In accordance with the present invention, a hydrolyzed, substantially hydrolyzed, or completely hydrolyzed carbohydrate-containing product may optionally thereafter be hydrogenated by contacting the hydrolyzed, substantially hydrolyzed, or completely hydrolyzed carbohydrate-containing product with either hydrogen or hydrogen mixed with a suitable gas along with a catalyst composition under a condition sufficient to form a hydrogenated product. In addition, in accordance with the present invention, a non-hydrolyzed carbohydrate-containing material may be hydrogenated by contacting the non-hydrolyzed carbohydrate-containing material with hydrogen or other suitable gas along with a catalyst composition under a condition sufficient to form a hydrogenated product.

Generally, suitable hydrolyzed, substantially hydrolyzed, or completely hydrolyzed carbohydrate-containing materials and/or non-hydrolyzed carbohydrate-containing materials include, but are not limited to, materials containing polysaccharides and/or monosaccharides, such as for example, dextrose, mannose, galactose, fructose and sucrose, and products derived from hydrolyzed polysaccharides such as starch.
Other suitable carbohydrate-containing materials, include, btit are not limited to, corn syrup and related products. Generally, any oxygenated hydrocarbon molecule may used in the present inventive process.

Useful catalysts in the present irivention include catalysts used to produce a hydrogenated product in the conversion of carbohydrates to hydrocarbons.
Generally, hydrogenation catalysts useful in the present invention include those containing an active metal on a support material. Examples of suitable metals include, but are not limited to, platinum, palladium, nickel, copper, iron, cobalt, zinc, lead, tin, mercury, ruthenium, combinations thereof, metal alloys of such metals, and oxides and chlorides of such metals.

The 'metal of the hydrogenation catalyst useful in the present invention is usually distributed over the surface of a support in a manner than maximizes the surface area of the metal. Examples of suitable support materials for the hydrogenation catalysts include, but are not limited to, silica, silica-alumina, alumimim oxide (A1203), silica-niagnesia, silica-titania and acidic zeolites of natural or synthetic origin.
The metal catalyst may be prepared by any method known in the art, including combining the metal with the support using conventional means including but not limited to impregnation, ion exchange and vapor deposition. In one embodiment of the present invention, the catalyst contains ruthenium supported on alumina. In another embodiment of the present invention, the catalyst contains ruthenium supported on an ion-exchange resin (such as for example, AmberliteTM 120(H) commercially available from Rohm and Haas). Generally, the use of an ion-exchange resin as the support may allow the conversion of a generally non-hydrolyzed carbohydrate-containing compound (such as for example, starch) to be hydrolyzed and hydrogenated in one step by contacting the non-hydrolyzed carbohydrate-containing compound with a ruthenium/ion-exchange resin catalyst under a condition sufficient to form a hydrolyzed/hydrogenated product.

The hydrogenation catalyst employed in the present invention may vary over a wide range and will depend upon the particular catalyst, carbohydrate, temperature and pressure which are employed in the process.

Reaction, or conversion, conditions for contacting a hydrolyzed, substantially hydrolyzed, or completely hydrolyzed carbohydrate-containing material and/or non-hydrolyzed carbohydrate-containing material includes a reaction temperature in the range of from about 80 C to about 300 C_ In another embodiment of the present invention, the temperature is in the range of from about 90 C to about 250 C. In another embodiment of the present invention, the temperature is in the range of from about 100 C to about 200 C.
In another embodiment of the present invention, the temperature is in the range of from about I 10 C to about 180 C.

The reaction, or conversion, conditions for contacting a hydrolyzed, 20. substantially hydrolyzed, or completely hydrolyzed carbohydrate-containing material and/or non-hydrolyzed carbohydrate-containing material includes a pressure in the range of from about 100 pounds per square inch gauge (psig) to about 2000 psig. In one embodiment of the present invention, the pressure is in the range of from about 550 to about 1900 psig. In another embodiment of the present invention, the pressure is in the range of from about 600 to about 1800 psig. In still another embodiment of the present invention, the pressure is in the range of from about 650 to about 1700 psig.

The carbohydrate-containing material may be contacted with a suitable gas, such as for example, hydrogen, in order to form a hydrogenated product. The gas may be introduced into the reaction chamber under pressure, which may vary with the nature of the reactants and the hydrogenation catalyst employed. The rate at which gas is charged to the reaction vessel is any suitable rate.
The time of reaction will depend upon the specific starting material, concentration, the specific catalyst used, pressure and temperature.
Generally, the duration of reaction is in the range of from about 20 minutes to about 120 minutes, which may be shorter or longer depending on the desired hydrogenation. The reaction is carried out in any suitable type of apparatus or reaction chamber which enable intimate contact of the reactants and control of the operating conditions. The process niay be carried out.in batch, semi-continuous, or continuous operation. In one embodiment of the present invention, a batch operation in a conventional autoclave is used. The reactants may be added to the reaction chamber in any suitable manner or in any suitable order. In one embodiment of the present invention, the hydrogenation catalyst is added fi'rst to the carbohydrate-containing solution , and thereafter, fed with hydrogen.

Liquid product from the hydrogenation step is believed to contain, among other things, polyhydric alcohols of the respective monosaccharide sugar. For example, when cornstarch (whose basic structural components consist of glucose units), is hydrolyzed and hydrogenated, the resulting reaction product contains the polyhydric alcohol-sorbitol.

In accordance with the present invention, a hydrogenated carbohydrate-containing product may be contacted with a suitable zeolite catalyst composition under a condition sufficient to produce a reaction product containing gasoline boiling range hydrocarbons. In addition, in accordance with the present invention, a non-hydrogenated carbohydrate-containing material may be contacted with a suitable zeolite catalyst composition.under a condition sufficient to produce a reaction product containing gasoline boiling range hydrocarbons. In accordance with the present invention, a hydrogenated carbohydrate-containing product, or a non-hydrogenated carbohydrate-containing product, or mixtures thereof, may be combined with an additional alkane, such as for example, iso-pentane, and thereafter, contacted with a suitable zeolite catalyst composition under a condition sufficient to produce a reaction product containing gasoline boiling range hydrocarbons.

Generally, suitable hydrogenated carbohydrate-containing products, or non-hydrogenated carbohydrate-containing products, or mixtures thereof, useful in the present invention, include but are not limited to, carbohydrate-containing materials that are hydrolyzed, substantially hydrolyzed, or completely hydrolyzed, and those that have not been hydrolyzed. In addition, suitable hydrogenated carbohydrate-containing products, or non-hydrogenated carbohydrate-containing products, or mixtures thereof, useful in the present invention, include, but are not limited to, materials containing polysaccharides and/or monosaccharides, such as for example, dextrose, mannose, galactose, fructose and sucrose, and products derived from hydrolyzed polysaccharides such a starch.
Other suitable carbohydrate-containing materials, include, but are not limited to, corn syrup and related products, as well as oxygenated hydrocarbon compounds, such as for example, lactic acid and sorbitol.

Carbohydrate-containing products, which may be hydrolyzed, hydrogenated, or both hydrolyzed and hydrogenated, or not hydrolyzed or hydrogenated, may be contacted with a catalyst composition containing a zeolite under a condition sufficient to produce a reaction product containing gasoline boiling range hydrocarbons. Useful catalyst compositions in the present invention include zeolites or zeolite material effective in the conversion of carbohydrates to hydrocarbons when contacted under suitable reaction conditions. Examples of suitable zeolites include, but are not limited to, those disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 15, pages 638-669 (John Wiley & Sons, New York, 1981). Generally, zeolites useful in the present invention have a constraint index (as defined in U.S. Pat. No. 4,097,367, which is incorporated herein by reference) in the range of from about 0.4 to about 12, and preferably in the range of from about 2 to about 9. In addition, the molar ration of Si02 to A1203 in the crystalline framework of the zeolite is at least about 5:1 and can range up to infinity. In one embodiment of the present invention, the molar ratio of Si02 to A1203 in the crystalline framework of the zeolite is in the range of from about 8:1 to about 200:1. In another embodiment of the present invention, Si02 to A1203 in the crystalline framework of the zeolite is in the range of from about 12:1 to about 100:1. Zeolites useful in the present invention include but are not limited to ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and combinations thereof. Some of these zeolites are also known as "MFI" or "Pentasil"
zeolites. In one embodiment of the present invention, the zeolite is ZSM-5.
Modified zeolites can also be used. Modified zeolites can include zeolites modified by metal cations, such as, for example, zinc, gallium, or nickel. Zeolites can also be modified by steam treatment and/or acid treatment. In addition, zeolites of the present invention may be combined with a clay, promoter, and/or a binder. Zeolites useful in the present invention may also contain an inorganic binder (also referred to as matrix material) selected from the group consisting of alumina, silica, alumina-silica, aluminum phosphate, clays (such as bentonite), and combinations thereof. The type of zeolite used will cause the final product to vary considerably.

Reaction, or conversion, conditions for contacting a carbohydrate-containing material, whether or not such material has been hydrolyzed and/or hydrogenated, includes a reaction temperature in the range of from about 100 C to about 1000 C. In another embodiment of the present invention, the temperature is in the range of from about 150 C to about 800 C. In another embodiment of the present invention, the temperature is in the range of from about 200 C to about 600 C. In another embodiment of the present invention, the temperature is in the range of from about 300 C to about 500 C. The i=eaction, or conversion, conditions for contacting a carbohydrate-containing material, whether or not such material has been hydrolyzed and/or hydrogenated, includes a pressure in the range of from about 1 pound per square inch gauge (psig) to about 500 pounds per square inch gauge (psig). In one embodiment of the present invention, the pressure is in the range of from about 3 to about 400 psig. In another embodiment of the present invention, the pressure is in the range of from about 5 to about 200 psig.

The carbohydrate-containing material, whether or not such material has been hydrolyzed and/or hydrogenated, may be contacted with a suitable gas, such as for example, hydrogen or nitrogen in order to form a product containing hydrocarbons. The gas may be introduced into the reaction chamber under pressure, which may very with the nature of the reactants and the zeolite catalyst employed. The flow rate may vary depending on the specific reaction conditions. In one embodiment of the present invention, the flow rate of gas is approximately in the range of 25 cc/min to 300 cc/min.

The time of reaction will depend upon the specific starting material, concentration, the specific catalyst used, pressure and temperature.
Generally, the duration of reaction is in the range of from about 0.01 to about 100 minutes, which may be shorter or longer depending on the desired hydrogenation. The reaction is carried out in any suitable type of apparatus or reaction chamber which enable intimate contact of the reactants and control of the operating conditions. The process may be carried out in batch, semi-continuous, or continuous operation. In one embodiment of the present invention, a batch operation in a conventional autoclave is used. The reactants may be added to the reaction chamber in any suitable manner or in any suitable order. In one embodiment of the present invention, the carbohydrate-containing solution is fed through the zeolite catalyst.
The process effluent, from the conversion zone, in accordance with the present invention, generally may contain gas and liquid fractions containing hydrocarbon products, which include, but are not limited to, a light gas fraction containing hydrogen, and methane, a C2-C3 fraction containing ethane, propane, ethylene, and propylene, an intermediate fraction including non-aromatic compounds having greater than 3 carbon atoms, a BTX aromatic hydrocarbons fraction (containing benzene, toluene, ortho-xylene, meta-xylene, and para-xylene) and a C9-C13 + fraction containing aromatic compounds having 9-13 or more carbon atoms per molecule.

In addition, the process effluent of the present invention, may also contain by products of carbon monoxide and carbon dioxide (CO,,). According to one embodiment of the present invention, the hydrocarbon product contain less COX, and less coke and other undesirable products are produced, when the reaction conditions are modified, for example, when the reaction conditions are at pressures generally in the range of from about 100 psig to about 200 psig. In addition, it has been discovered that higher reaction pressures, preferably at about 200 psig, result in the production of less COx(preferably less than about weight percent of the product), less coke, and upgrading of the hydrocarbon stream to a higher-octane gasoline.

The following examples are presented to further illustrate the present invention and are not to be construed as unduly limiting the scope of this invention.

This example illustrates the increased solubility of starting carbohydrate materials, such as for example, polysaccharides such as starch, when treated with ion-exchange resins in accordance with the present invention.

Run 1 (Control) 25 As shown in Table I-A below, a 40.02 gram sample of solid corn starch (commercially available from retail sources) was mixed with 100 mL of water by stirring.
The starch/water solution was loaded to 300cc in an autoclave, and the system was flushed with nitrogen and sealed. The mixture was then heated to 140 C at about 50 psig and held for approximately 30 minutes while stirring. The mixture was then allowed to cool to room temperature and the mixture was discharged from the autoclave. It was observed that the corn starch in Run I did not dissolve in water after heating.

Run 2 (Control) As shown in Table I-A, a 40.02 gram sample of solid corn starch (commercially available from retail sources) was mixed with 100 mL of carbonated water (from club soda). The starch/ club soda solution was loaded to 300cc in an autoclave, and the system was flushed with nitrogen and sealed. The mixture was then heated to 140 C at about 50 psig and held for approximately 30 minutes while stirring. The mixture was then allowed to cool and the mixture was discharged from the autoclave. It was observed that the corn starch in Run 2 did not dissolve in slightly acidified water after heating.

Run 3 (Invention) As shown in Table I-A, a 40.02 gram sample of corn starch (commercially available from retail sources) was added to 100 mL water, along with 1.0 gram of AmberliteTM IR-120(H) (commercially available from Rohm and Haas) and was mixed by stirring. The corn starch/water/AmberliteTM mixture was loaded into an autoclave and flushed with nitrogen and sealed, and thereafter was heated to approximately 140 C at about 50 psig and held for approximately 30 minutes while stirring. After cooling down and, discharging the materials from the autoclave, it was observed that 100 % of the com starch dissolved in watet. Dextrose Equivalence tests (DE) were run after treatment to measure the extent of hydrolysis. The DE results suggested that about 50 to about 80 percent of the com starch was converted to the monosaccharide sugar dextrose after heating in the presence of the ion exchange resin.
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EXAMPLE II

This example illustrates a process of converting carbohydrates to gasoline boiling range hydrocarbons (such as for non-aromatic and aromatic gasoline boiling range hydrocarbons) including hydrolyzing the carbohydrate-containing product, hydrogenating the product, and then converting the product over a zeolite catalyst.

Step 1 - Dissolution Run 3 from Example I was repeated two (2) additional times, and the liquid product from all three (3) runs was pooled together, as shown in Table 11-A
below.

Table 11-A - Carbohydrate Dissolution Step Carbohydrate Liquid Temperature/ Ion Exchange Resulting medium Pressure Resin product Starch Water AmberliteTM Liquid; 100%
1 (40.02g) (100mL) 140 C 150 psig* IR-120(H)(1 g) dissolved *Note - autoclave was not pressurized before heating; pressure increase is due to vapor pressure of water at heated temperature.

Step 2 - Hydrogenation-The liquid product from step 1, along with hydrogen gas, was fed through a Ru/A1203 catalyst at 140 C and 150 psig as shown in Table II-B below:

Table 11-B - Hydromation Step Gas Feed Liquid Feed Temperature/ Hydrogenation Resulting Pressure Catal st product liquid product 2 Hydrogen from step 1(15 140 C /150 psig Ru/A1203 Liquid (300 cc%min) cc/hour) hydrogenated liquid product was collected and used for the liquid feed in step 3 below.
Step 3 - reaction of product over ZSM-5 The hydrogenated liquid product from Step 2 was collected and used as feed, and reacted over ZSM-5 catalyst as shown in Table II-C below. Both the gas phase and liquid phase products were analyzed to deterrnine the hydrocarbon product distribution.

Table II-C- reaction of product over ZSM-5 Step Gas Liquid Feed Temperature/ Second Resulting product Feed Pressure Catalyst liquid product from ZSM-5 *See product 3 n/a step 2 (26 cc/hour) 400 C /10 psig (8.0 g) distribut andl ITable Table Table II-D - Hydrocarbon product distribution (includes both gas and liquid phase) Carbon C1 C2= C2 C3= C3 C4= C4 C5+
Number Weight 0.35 3.71 I .020 7.59 I .032 2.58 0.98 84.27 Percent Table II-E - Liquid Phase Hydrocarbon Product Analyzed by DHA method Carbon Number/Group Weight percent C5 0.021 C6 0.366 C7 5.096 C8 17.353 C9 15.014 C 10 15.756 C11 9.123 C12 3.997 -C13+ 12.215 Aromatics 58.499 Paraffin 0.708 i-Paraffin 4.994 Naphthenes 1.177 Unidentified 21.059 -Plus 12.157 Olefins 1.406 EXAMPLE III

This example illustrates a process of converting corn syrup to gasoline boiling range hydrocarbons (such as for non-aromatic and aromatic gasoline boiling range hydrocarbons) including hydrogenating the com syrup, and then converting the product over a zeolite catalyst.

Step 1 - Hydrogenation of Corn Syrun A corn syrup/water (50 wt %/ 50 wt %) solution and hydrogen gas were fed through a Ru/AlZ03 catalyst at 200 F and 150 psig as shown in Table III-A
below:

Table III-A - Hydrogenation of Corn Syrup Step Gas Feed Corn Syrup/Water Temperature/ First Resulting Feed Pressure Catalyst product Com Syrup/Water (300 ccg/min) Feed (50 wt %/50 200 F /150 psig Ru/Al203 Liquid wt /0 (13.13 cc/hr The hydrogenated liquid product was collected and used for the liquid feed in step 2 below.

Step 2- Conversion over ZSM-5 The hydrogenated liquid product was collected and used as feed, and reacted over ZSM-5 catalyst as shown in the table below. Both the gas phase and liquid phase products were analyzed by gas chromatography to determine the hydrocarbon product distribution.

Step Gas Liquid Feed Temperature/ Second Resulting product Feed' Pressure Catalyst Product from Step I *See product distribution 2 n/a (24 cc/hour) 400 C/10 psig 8.0 g ZSM-5 in Table Ill-B and Table III-C below Table III-B - Hydrocarbon product distribution (includes both gas and liquid phase) Carbon Cl C2= C2 C3= C3 C4= C4 C5+
Number Weight 1 0.15 3.01 0.1 4.43 0.35 11.52 0.25 90.19 Percent Table 111-C - Liquid Phase Hydrocarbon Product Analyzed by DHA method Carbon Number/Group Weight percent C5 0.019 C6 0.932 C7 10.098 C8 23.377 C9 14.71 C 10 12.764 C11 9.045 C12 3.161 C13+ 6.815 Aromatics 69.52 Paraffin 0.36 i-Paraffin 2.66 Naphthenes 0.77 Unidentified 19.08 Plus 6.77 Olefins. 0.85 EXAMPLE IV

This example illustrates a process of converting hydrogenated carbohydrates, specifically, sorbitol, to gasoline boiling range hydrocarbons (such as for non-aromatic and aromatic gasoline boiling range hydrocarbons) by combining sorbitol with iso-pentane, and reacting the mixture over ZSM-5 catalyst.

In this example, a sorbitol/water/iso-pentane mixture was co-fed along with hydrogen gas through a ZSM-5 zeolite. As shown in the Table IV-A, conversions of sorbitol and iso-pentane were observed.. The liquid product was rich in aromatics and the gas phase product was rich in olefins. ' About 28 weight percent of the product was C2-C4 olefins, 16 weight percent CO,e, 51 weight percent C5+ and 5 weight percent C1-C4 paraffins. For the liquid product, about 83% were aromatics with most being C7 or C8.
Table IV-A - Sorbitol + Iso-pentane Feed I HC-liquid Feed 2 Gas Feed Temp. Catalyst Resulting product *See product Sorbitol (28.6 wt %) distribution I-CS %) H2 C 8.0 g ZSM-5 in Table (density -.62 g/mL) Water density (7(11.1.4 03 wt gImL) (150 mWmin) 500 IV-B, Table IV-C,and Table IV-D
below.
Table IV-B - Reactant % Conversion Reactant %
Conversion Sorbitol 95.93 I-C5 19.41 Table IV-C - Liquid Phase Hydrocarbon Product Analyzed by DHA method Carbon Number/Group Weight percent C4 0.3 C5 1.7 C6 6.4 C7 25.4 C8 30.6 C9 8.2 C10 9.8 Ci l 6.0 C12+ 4.1 Aromatics 83.1 Paraffin 0.5 i-Paraffin 2.1 Naphthenes 0.7 Unidentified 7.5 Plus 2.9 Olefins 3.3 Table IV-D - Product selectivity Group Carbon mole %
Cl-C4 paraffins 5.0 C2-C4 olefins 28.4 C5+ 50.6 COx 16.0 EXAMPLE V

This example illustrates the effect of pressure on the hydrocarbon product stream resulting from the conversion of carbohydrates to gasoline boiling range hydrocarbons (such as for non-aromatic and aromatic gasoline boiling range hydrocarbons).
As shown in Table V-A below, with the increase in reaction pressure, the conversion of sorbitol (used in this example) was 99 weight percent. With an increase in pressure, there was an increase in CI-C4 paraffins, a decrease in C2-C4 olefins, a decrease in coke, and increase in C5+, and a decrease in the amount of sorbitol carbon converted to CO,t. In addition, Table V-A shows that at higher pressures, more of the oxygen in sorbitol is removed as water with iso-pentane acting as the hydrogen donor. In addition to reducing the CO,, yield from sorbitol, higher pressures result in upgrading of iso-pentane to a higher-octane gasoline.
Table V - Effect of reaction pressure on hydrocarbon product Run 1 2 3 Pressure, psig 20 100 200 Temperature, C 500 500 500 N2 flow rate, 25 125 250 mL/min.
Catalyst ZSM-5 ZSM-5 ZSM-5 Feed I(11 mL/hr) Sorbitol/H20 Sorbitol/H20 (50:50) Sorbitol/H20 (50:50) 50:50) Feed II (6.5 mL/hr) IC-5 IC-5 IC-5 Sorbitol conversion 99.0 99.0 99.0 %
I-C-5 conversion % 26.0 55.1 55.0 Product distribution C mole % per run C 1-C4 araffins 5.3 11.3 15.7 C2-C4 olefins 12.6 7.4 7.5 C5+ 53.1 59.9 59.9 Coke 7.3 .5.1 4.9 COx 21.7 16.3 12.0 Sorbitol C to CO, % 29.2 28.0 20.8 EXAMPLE VI

This example illustrates a process of converting oxygen-containing hydrocarbons, specifically, lactic acid, to gasoline boiling range hydrocarbons (such as for non-aromatic and aromatic gasoline boiling range hydrocarbons) using a ZSM-5 catalyst.

In this example, lactic acid was converted to gasoline range hydrocarbons and chemicals (light olefins) as shown in Table VI-A below. The lactic acid conversion was 78.7 percent with selectivity to CI=C4 paraffins, C2-C4 olefins, C5+ hydrocarbons.

Table VI-A - Lactic Acid conversion Feed Gas Feed Temp. Catalyst Lactic Acid Resulting conversion /o product 85% lactic acid in N2 *See product water (100 500 C 6.0 g ZSM-5 78.7% distribution (20 inL/hour) mI./min) in Table VI-B below Table VI-B - Product selectivity Group Carbon mole %
C 1-C4 araffins 4.0 C2-C4 olefins 15.6 C5+ (mainly aromatics) 42.5 Cox 38.0 The results shown in the above examples, clearly demonstrate that the present invention is well adapted to carry out the objects and attain the ends and advantages mentioned as well as those inherent therein. Reasonable variations, modifications and adaptations may be made within the scope of this disclosure and the appended claims without departing from the scope of the invention.

Claims (68)

1. A process comprising:
contacting a carbohydrate-containing material with an ion-exchange resin in a liquid medium to form a mixture; and heating the mixture at a temperature sufficient to substantially dissolve the carbohydrate-containing material in the liquid medium.
2. The process of claim 1, wherein said carbohydrate-containing material has an effective hydrogen to carbon ratio of less than about one.
3. The process of claim 1, wherein said carbohydrate-containing material is a polysaccharide.
4. The process of claim 1, wherein said carbohydrate-containing material is selected from the group consisting of starch, cellulose, glycogen and mixtures thereof.
5. The process of claim 1, wherein said carbohydrate-containing material is starch.
6. The process of claim 1, wherein said ion-exchange resin comprises a strongly acidic cation-exchange resin.
7. The process of claim 1, wherein said ion-exchange resin contains sulfonic groups.
8. The process of claim 1, wherein said ion-exchange resin is present in an amount in the range of from about .02 to about 10 weight percent, based on the weight of the mixture.
9. The process of any of claims 1 - 8, wherein said temperature is in the range of from about 100°C to about 180°C.
10. The process of claim 9, wherein said temperature is in the range of from about 120°C to about 160°C.
11. The process of claim 9, wherein said temperature is in the range of from about 120°C to about 140°C.
12. The process of any of claims 1 - 8, wherein said contacting comprises loading the mixture into an autoclave, flushing the autoclave with nitrogen, and sealing the autoclave.
13. The process of any of claims 1 - 8, wherein said heating comprises heating the mixture at a temperature in the range of from about 100°C to about 180°C until the mixture is dissolved.
14. The process of any of claims 1 - 8, wherein said liquid medium is water.
15. The process of any of claims 1 - 8, wherein said ion-exchange resin is a polystyrene supported resin containing sulfonic acid groups.
16. The process of any of claims 1 - 8, wherein between 95% and 100% of said carbohydrate-containing material is dissolved in said liquid medium.
17. A process comprising:
contacting a carbohydrate-containing material with an ion-exchange resin in a liquid medium under a condition sufficient to substantially dissolve the carbohydrate-containing material in the liquid medium to form a mixture, contacting the mixture with a hydrogenation catalyst under a condition sufficient to form a hydrogenated product, and contacting a mixture comprising the hydrogenated product with a catalyst composition comprising a zeolite under a condition sufficient to form a reaction product containing gasoline boiling range hydrocarbons.
18. The process of claim 17, wherein said carbohydrate-containing material has an effective hydrogen to carbon ratio of less than about 1.
19. The process of claim 17, wherein said carbohydrate-containing material is a polysaccharide.
20. The process of claim 17, wherein said carbohydrate-containing material is selected from the group consisting of starch, cellulose, glycogen and mixtures thereof.
21. The process of claim 17, wherein said carbohydrate-containing material is starch.
22. The process of claim 17, wherein the ion-exchange resin comprises an acidic cation-exchange resin.
23. The process of claim 17, wherein the ion-exchange resin contains sulfonic groups.
24. The process of claim 17, wherein said ion-exchange resin is present in an amount in the range of from about .02 to about 10 weight percent, based on the weight of the mixture.
25. The process of any of claims 17 - 24, wherein said condition sufficient to substantially dissolve the carbohydrate-containing material in the liquid medium to form a mixture comprises a temperature in the range of from about 100°C to about 180°C and a pressure in the range of from about 10 to about 500 psig.
26. The process of any of claims 17 - 24, wherein said hydrogenation catalyst comprises a supported ruthenium catalyst.
27. The process of any of claims 17 - 24, wherein said condition sufficient to form a hydrogenated product comprises a temperature in the range of from about 80°C to about 300°C and a pressure in the range of from about 100 to about 2000 psig.
28. The process of any of claims 17 - 24, wherein said condition sufficient to form a reaction product containing gasoline boiling range hydrocarbons comprises a temperature in the range of about 200°C to about 800°C and a pressure in the range of from about 1 to about 500 psig.
29. The process of any of claims 17 - 24, wherein said contacting comprises loading the mixture into an autoclave, flushing the autoclave with nitrogen, and sealing the autoclave.
30. The process of any of claims 17 - 24, wherein said heating comprises heating the mixture at a temperature in the range of from about 100°C to about 180°C until the mixture is dissolved.
31. The process of any of claims 17 - 24, wherein said liquid medium is water.
32. The process of any of claims 17 - 24, wherein said ion-exchange resin is a polystyrene supported resin containing sulfonic acid groups.
33. The process of any of claims 17 - 24, wherein between 95% and 100% of said carbohydrate-containing material is dissolved in said liquid medium.
34. The process of-any of claims 17 - 24, wherein said hydrogenated product is selected from the group consisting of ketones, epoxides, diols, glycols, furans, and organic acids.
35. The process of any of claims 1-7 - 24, wherein said hydrogenated product is lactic acid.
36. The process of any of claims 17 - 24, wherein said hydrogenated product is sorbitol.
37. The process of any of claims 17 - 24, wherein said mixture further comprises a hydrocarbon.
38. The process of claim 37, wherein said hydrocarbon is isopentane.
39. A process in accordance with any of claims 17 - 24, wherein said zeolite is selected from the group consisting of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, and combinations thereof.
40. A process in accordance with any of claims 17 - 24, wherein said zeolite is ZSM-5.
41. A process in accordance with any of claims 17 - 24, wherein said zeolite is modified by steam treatment.
42. A process in accordance with any of claims 17 - 24, wherein said zeolite is modified by acid treatment.
43. A process in accordance with any of claims 17 - 24, wherein said zeolite is modified by a metal cation.
44. A process in accordance with claim 43 wherein said metal cation is selected from the group consisting of zinc, gallium, and nickel.
45. A process comprising:
contacting an aqueous solution containing at least one carbohydrate with a hydrogenation catalyst under a condition sufficient to form a hydrogenated product, and contacting the hydrogenated product with a catalyst composition comprising a zeolite under conditions sufficient to form a reaction product containing gasoline boiling range hydrocarbons.
46. The process of claim 45, wherein the aqueous solution contains corn syrup.
47. The process of claim 45, wherein the hydrogenation catalyst comprises a supported ruthenium catalyst.
48. The process of claim 45, wherein the conditions sufficient to form a hydrogenated product comprises a temperature n the range of from about 80°C to about 300°C and a pressure in the range of from about 100 to about 1000 psig.
49. A process in accordance with any of claims 45 - 48, wherein said zeolite is selected from the group consisting of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, and combinations thereof.
50. A process in accordance with any of claims 45 - 48,wherein said zeolite is ZSM-5.
51. A process in accordance with any of claims 45 - 48, wherein said zeolite is modified by steam treatment.
52. A process in accordance with any of claims 45 - 48, wherein said zeolite is modified by acid treatment.
53. A composition produced by the process of any of claims 45 - 48,
54. A process comprising:

contacting a mixture comprising an oxygen-containing hydrocarbon compound with a catalyst composition comprising a zeolite under a reaction conditions sufficient to form a reaction product containing gasoline boiling range hydrocarbons.
55. The process of claim 54, wherein the oxygen-containing hydrocarbon compound is sorbitol.
56. The process of claim 54, wherein said oxygen-containing hydrocarbon is lactic acid.
57. The process of claim 54, wherein said mixture further comprises a hydrocarbon.
58. The process of claim 54, wherein said hydrocarbon comprises isopentane.
59. The process of claim 54, wherein said oxygen-containing hydrocarbon compound is selected from the group consisting of ketones, epoxides, diols, glycols, furans, and organic acids.
60. A product produced by the process of claim 54.
61. The process of any of claims 54 - 59, wherein the condition sufficient to form a reaction product containing gasoline boiling range hydrocarbons comprises a temperature in the range of about 200°C to about 600°C and a pressure in the range of from about 1 to about 100 psig.
62. The process of any of claims 54 - 59, wherein the reaction conditions comprise a pressure in the range of from about 20 to about 200 psig.
63. A process in accordance with of any of claims 54 - 59, herein said zeolite is selected from the group consisting of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, and combinations thereof.
64. A process in accordance with of any of claims 54 - 59, wherein said zeolite is ZSM-5.
65. A process in accordance with of any of claims 54 - 59, wherein said zeolite is modified by steam treatment.
66. A process in accordance with of any of claims 54 - 59, wherein said zeolite is modified by acid treatment.
67. A process in accordance with of any of claims 54 - 59, wherein said zeolite is modified by a metal cation.
68. A process in accordance with claim 67, wherein said metal cation is selected from the group consisting of zinc, gallium, and nickel.
CA2633446A 2005-12-16 2006-12-14 Process for converting carbohydrates to hydrocarbons Active CA2633446C (en)

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CA2808278C (en) 2015-02-24
CA2808278A1 (en) 2007-07-05
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