NZ624647B2 - Synthesis of high caloric fuels and chemicals - Google Patents

Abstract

Disclosed herein are methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Particularly, the specification discloses a method for the preparation of an alkyl compound or a mixture of alkyl compounds, the method comprising: a) preparing a ketene of the formula I: b) reacting the ketene in a self-addition reaction to form a diketene of the formula II; and c) hydrogenating the diketene of the formula II in the presence of a metal catalyst to form the alkyl compound or the mixtures of alkyl compounds. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc. : a) preparing a ketene of the formula I: b) reacting the ketene in a self-addition reaction to form a diketene of the formula II; and c) hydrogenating the diketene of the formula II in the presence of a metal catalyst to form the alkyl compound or the mixtures of alkyl compounds. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.

Description

SYNTHESIS OF HIGH CALORIC FUELS AND CHEMICALS RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 61/558,321 filed November 10, 2011 entitled "Synthesis of Higher ls", U.S. Provisional Application No. 61/577,903 filed December 20, 2011 entitled "Higher Calorific Alcohol and Alkane Fuels and rial Chemicals", U.S. Provisional Application No. 61/614,937 filed March 23, 2012 entitled "Synthesis of Hydrocarbon and ated Fuels and Chemicals", U.S. Provisional ation No. 61/643,447 filed May 7, 2012 entitled tive Syngas sion to Butanol” and U.S. Provisional Application No. 61/667,093 filed July 2, 2012, entitled esis of C5 and C6 Fuels and Chemicals”, all of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION Petroleum is a vital source of fuels for transportation, industrial chemicals that produce polymers, plastics, pharmaceuticals, paints and other ant chemicals. However, due to economic, environmental and political factors, new sources besides petroleum are being sought for the tion of these materials.

Technologies to manufacture industrial commodities such as methanol are mature and used to produce the world’s supply from synthesis gas that comes from methane, coal, etc.

Ethanol is produced by fermentation and hydration of ethylene produced from petroleum.

Technology to produce ethanol from cellulose is still in development. s have been made to develop a synthesis of ethanol from synthesis gas but no satisfactory technologies have materialized yet. There has been increased use of ethanol as a fuel ve and also as an automotive fuel itself. Ethanol does not have a high heat of combustion (30 MJ/kg ethanol vs 45 MJ/kg gasoline) thus yielding significantly lower mileage than gasoline. Another issue with ethanol is the difficulty of ethanol transport by pipeline due to its corrosivity.

Various efforts are underway to find economic fermentation processes to produce butanol which is also an important fuel alternative and industrial chemical. However the economy of these ses due to the time required for each fermentation cycle, environmental problems from large amounts of water consumption for these processes and difficulty of isolation of butanol from broths along with its toxicity to es are challenges that have not been overcome.

It is an object of the present invention to avoid these issues and to provide a novel method to synthesize fuels and als from non-petroleum sources such as biomass, coal and natural gas; and/or to provide the public with a useful choice. The synthetic manufacture of fuels and chemicals, for example alcohols and alkanes with four or more carbons, offers the potential for higher energy fuels that are readily compatible with existing automotive and ortation infrastructure.

BRIEF DESCRIPTION OF DRAWINGS Fig. 1 shows a representative method for the synthesis of l from acetic acid via Fig. 2 shows a representative method for the synthesis of higher alcohols and hydrocarbons from acetic acid via a diketene.

Fig. 3 shows a representative method for the synthesis of butanol from diketene via a beta-butyrolactone intermediate.

Fig. 4 shows a representative method for the synthesis of butanols from acetic acid via an acetoacetate ester intermediate.

Fig. 5 shows a representative method for the synthesis of dehydroacetic acid from synthesis gas.

Fig. 6 shows a representative method for the synthesis of seven carbon alcohol from ketene via oacetic acid.

Fig. 7 shows a representative method for the sis of alcohols and hydrocarbons from ketene via dehydroacetic acid.

Fig. 8 shows a representative method for the synthesis of heptanol and heptanes via ketonization of butyric acid formed by reduction of diketene.

Fig. 9 shows a representative method for the synthesis 2-methyl pentanol from ethanol.

Fig. 10 shows a entative method for the synthesis of hydrocarbons from methyl ketene.

Fig. 11 shows a representative method for the synthesis of pentanol from ethanol.

Fig. 12 shows a representative method for the synthesis of l-propanol fuel from ethanol or methanol.

Fig. 13 shows a representative method for the synthesis of higher ls from methanol via reductive carbonylation.

Fig. 14 shows a representative hydrogenation r system.

Fig. 15 shows a representative reactor system for lab scale synthesis of diketene.

Fig.16 shows a representative reactor system for lab scale synthesis of dimer of methyl ketene.

Fig. 17 is a representative description of a r system used for hydrogenation of dehydroacetic acid.

Fig. 18 is a representative description of a reactor system used for ketonization and hydrogenation reaction steps. [0023a] Fig. 19 is a graph showing product composition change with time and ature in Run 11 DHAA hydrogenation. [0023b] Fig. 20 is a graph showing the bution of products over time as temperature is varied for butyric acid ketonization-hydrogenation.

DETAILED DESCRIPTION OF THE INVENTION In a first ment, the invention provides a method for the preparation of an alkyl nd or a mixture of alkyl compounds, the method comprising: a) preparing a ketene of the formula I: wherein: each R1 is independently H or C1-6 alkyl; and each R2 is independently H or C1-6 alkyl; b) reacting the ketene in a self-addition reaction to form a diketene of the formula II; c) hydrogenating the diketene of the formula II in the presence of a metal catalyst to form the alkyl compound or the mixtures of alkyl compounds.

] In a second embodiment, the invention provides alkane compounds prepared by the method of the invention. [0024b] In a third embodiment, the invention provides a fuel composition comprising the alkane compounds of the invention. [0024c] Also bed is a process of using a ketene to form a diketene which is then reduced by hydrogen to form l and hydrocarbon fuel and chemical raw materials. In one aspect, an acid, such as a two carbon acetic acid, is converted to a ketene which is dimerized and d to products with four or more carbons such as butanol, heptanol and other alcohols. The alcohols produced include compounds, such as alcohols, with three to nine carbons including butanol and its isomers, pentanol and its isomers, l and its isomers, heptanol and its isomers, etc may be used as fuels which have a calorific values closer to gasoline.

Also described is a process of using syngas as a feedstock to produce diketene which is then selectively hydrogenated to butanol via intermediate beta-butyrolactone. Ketene may be prepared from methanol, which may be carbonylated to form acetic acid and dehydrated to form ketene. In another aspect, the s provides diketene which is then selectively hydrogenated to butanol via an intermediate acetoacetate ester such as methyl acetoacetate. Diketene is y produced from acetic acid by dimerization of ketene, ketene is produced by pyrolysis of acetic acid and acetic acid is manufactured from syngas via carbonylation of methanol. The alcohol products produced, such as 2-butanol and nol and heptanols have a calorific value closer to gasoline than ethanol. The 1-butanol and 2-butanol product produced by the methods described herein may be used individually or as mixtures.

Also disclosed is a process for ting ketene to diketene, ting diketene to dehydroacetic acid (3-acetylhydroxymethyl-4H-pyranone, “DHAA”) and reduction of DHAA to heptanols, heptanones or heptanes and other useful higher alcohols and alkanes.

Diketene is prepared from acetic acid which can in turn be synthesized by the ylation of methanol or the oxidation of ethanol. The ls produced, such as 4-heptanol and some of its s and other products such as pentanol and its isomers, l and its isomers, l and its isomers, heptanes and other alkanes, etc which may be used as fuels, have significantly higher calorific values close to gasoline and higher than ethanol and butanol fuel.

Also described is a process to convert two carbon acetic acid to seven carbon products like heptane, heptanone and heptanol using ketene, ketonization and hydrogenation chemistry. sis gas is converted to acetic acid which is dehydrated to form ketene which is dimerized to form diketene. Diketene is converted to butyric acid which is ketonized to form 4-heptanone. 4-Heptanone may be reduced to 4-heptanol or heptanes and other useful higher alcohols and alkanes. The resulting products, such as 4-heptanol, heptane, etc … which may be used as fuels, have significantly higher calorific values close to gasoline and higher than ethanol and butanol fuel. In another aspect, the heptanol prepared according to the processes are highly ive, and produces at least 60%, 65% or 80% heptanol. The ts comprising es of four or more carbon alcohols and alkanes are much more le to transport h existing pipeline structures.

Also described is a process to convert ethanol to C5-6 alcohols, including 3-pentanol and 2-methylpentanol. In one embodiment ethanol is carbonylated to form propanoic acid which is ated to form methyl ketene, methyl ketene is dimerized to form 2-methylethylideneoxetanone which is hydrogenated to form 2-methyl ol. In one embodiment, ethanol is carbonylated to form propanoic acid, propanoic acid is ketonized to form 3-pentanone and 3- pentanone is reduced to form 3-pentanol. In one aspect of the method, the fuel composition is blended with an automotive fuel.

In each of the product or product mixtures prepared according to the above processes, the products may also be used as solvents and chemicals in industry. In addition, the products may be blended with fuels such as ne, diesel or like fossil fuels or with a biofuel or synthetic fuels, and combinations thereof.

DEFINITIONS: Unless specifically noted otherwise herein, the definitions of the terms used are standard definitions used in the art. Exemplary embodiments, aspects and variations are illustrated in the s and drawings, and it is ed that the embodiments, aspects and variations, and the figures and drawings disclosed herein are to be considered illustrative and not limiting. [0030a] The term ising” as used in this specification and claims means “consisting at least in part of”. When interpreting statements in this ication, and claims which include the term “comprising”, it is to be understood that other features that are additional to the features prefaced by this term in each statement or claim may also be present. Related terms such as “comprise” and “comprised” are to be interpreted in similar manner.

As used , an "alkyl" group is a straight, branched, cyclic, acylic, saturated or unsaturated, aliphatic group or alcoholic group having a chain of carbon atoms. A C1-C20 alkyl or C1-C20 alkanol, for example, may include alkyl groups that have a chain of between 1 and 20 carbon atoms, and include, for example, the groups methyl, ethyl, propyl, isopropyl, vinyl, allyl, enyl, isopropenyl, ethynyl, 1-propynyl, 2-propynyl, 1,3-butadienyl, penta-1,3-dienyl, penta-1,4-dienyl, hexa-1,3-dienyl, hexa-1,3,5-trienyl, and the like. An alkyl group may also be represented, for example, as a -(CR1R2)m- group where R1 and R2 are independently hydrogen or are independently absent, and for e, m is 1 to 8, and such representation is also intended to cover both saturated and unsaturated alkyl groups.

An “alkyl compound(s)” as used herein, is an alkyl containing 1 to 20 carbons (C1-C20 alkyl), and includes cyclic and acyclic alkanes, alkenes, alcohols, ketones and aromatics (e.g., benzene, toluene, ethyl benzene etc.) and mixtures thereof. The alkyl compound may be used as a raw material for chemical processing, a solvent or the alkyl compound may be used as a fuel or mixtures of fuels. Such fuel or mixtures of fuels may be further combined with other fuel or fuel ts to form a gasoline. Non-exclusive es of an alkyl compound include butane, 1- butanol, 2-butanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-heptanol, 4-heptanol, anone, 3- methyl cyclohexanol, 2,6-dimethylheptanol and mixtures f. Alkyl compounds of the present application exclude saturated beta-lactones.

A "cyclyl" such as a clyl or polycyclyl group includes monocyclic, or ly fused, angularly fused or bridged polycycloalkyl, or ations thereof. Such cyclyl group is intended to include the heterocyclyl analogs. A cyclyl group may be saturated, lly saturated or aromatic.

An alkanol or an alcohol is a compound with an alkyl or cyclic alkyl group bearing a hydroxyl group. Examples of alcohols are ol, ethanol, propanol, panol, butanol (including 1-butanol, 2-butanol, isobutanol, tert-butanol), pentanol (and its isomers including 1- pentanol, 2-pentanol, anol, isopentanol, neopentanol, cyclopentanol, etc) and straight chain, branched and cyclic isomers of other higher alcohols such as hexanol, cyclohexanol, methylcyclohexanol, heptanol (including 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, isoheptanol and other isomers), nonanol, etc. A higher alcohol is an alcohol having two or more carbons.

“Gasoline” is known to comprise of a complex mixture of volatile arbons le for use as a fuel in a spark-ignition internal combustion engine. lly, gasoline boils over a range of about 27 °C to about 225 °C. Gasoline may consist of a single blendstock, such as the product from a refinery alkylation unit, or it may comprise of a blend of several blendstocks. The blending of gasoline is well kown in the art and may include a combination of three to twelve or more different blendstocks. Optimization of the blending process takes into account a plurality of characteristics of both the blendstocks and the resulting gasoline, and may include such characteristics as cost and s measurements of volatility, octane, boiling point characteristics and al composition. While hydrocarbons usually represent a major component of gasoline, n oxygen containing organic compounds may be included as gasoline components. In one aspect, such oxygen containing organic nds are ed to as "oxygenate" or "oxygenates," and are important gasoline substitutes such as ethanol and butanol. Oxygenates are also useful as components in gasoline because they are y of high octane and can be a more economical source of gasoline octane than a high octane hydrocarbon blending component such as te or reformate. Oxygenates that may be used as gasoline blending agents e, but are not limited to, methanol, ethanol, tertiary-butyl alcohol, methyl tertiary-butyl ether, ethyl tertiary-butyl ether and methyl tertiary-amyl ether. Various catalysts may be used in reduction or enation ons of the present application. The catalyst used may contain one or more transition metal such as ruthenium, palladium, platinum, rhodium, nickel, m, rhenium, copper, zinc, chromium, nickel, iron, cobalt or combinations of thereof.

The catalyst may contain a combination of one or more tion metals with main group elements such as for example platinum and tin or ium and tin. The catalyst may contain promoters such as barium hydroxide, magnesium hydroxide, etc. Reduction or hydrogenation may also be done using Raney type sponge catalysts such as Raney nickel, copper, cobalt, etc optionally bearing promoters such as iron, molybdenum, chromium, palladium, etc.

Catalysts used in reductions may be ted or unsupported. A supported catalyst is one in which the active metal or metals are deposited on a support material; e.g. prepared by g or wetting the support material with a metal solution, spraying or physical mixing followed by drying, ation and finally reduction with hydrogen if necessary to produce the active catalyst. Catalyst support materials used frequently are porous solids with high surface areas such as silica, alumina, titania, magnesia, carbon, zirconia, zeolites etc.

The methods described herein can comprise, consist of, or consist essentially of the essential ts and limitations of the method described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in synthetic organic chemistry.

“Synthesis gas” or “syngas” is a mixture of varying amounts of carbon monoxide and hydrogen. Syngas maybe produced by the partial oxidation of materials such as methane, liquid hydrocarbons, coal, biomass, etc.

“Biomass” is material obtained from living or recently living organisms.

Acetic acid may be made by ion of ethanol produced by fermentation or conversion of synthesis gas to methanol followed by its ylation. Synthesis gas may be obtained in large quantities from biomass, coal, natural gas, etc.

In one embodiment acetic acid used in the s described herein is made from . Syngas may be made from coal, natural gas or like fossil fuel. In another embodiment the acetic acid used in the invention is synthesized from syngas made from a ble source such as biomass from corncobs, switchgrass, wood chips, recyclable materials like agricultural waste, land fill materials, rial waste, municipal solid waste, sewage and the like.

Ketene maybe sized by various methods described in literature such as ation of acetic acid, pyrolysis of acetone or acetic ide, etc. In one embodiment ketene is synthesized from acetone. In another embodiment ketene is synthesized from acetic acid. In one embodiment, the ketene produced is dimerized to produce diketene which can be used directly in reduction steps or stored before reduction.

Also described are methods to prepare alcohols from ketene and diketene. Ketene is dimerized to form diketene which is reduced to e alcohols and carbon nds such as hydrocarbons which can be used as fuels and chemicals for industry. In another embodiment diketene is hydrogenated to form a four carbon alcohol. In one embodiment, the product of hydrogenation is a mixture of 2-butanol and 1-butanol. In another embodiment, the hydrogenation product of diketene reduction is a mixture of alcohols including isomers of butanols, ols, hexanols, heptanol and higher and lower alcohols. These products may be used as a fuel directly or after purification.

Products such as butyric acid seen in the products of the invention (see Table 5a below) have lower calorific values than alcohols and hydrocarbons but are highly useful for conversion to seven carbon heptanol and heptanes and other high energy fuels and useful chemicals by ketonization and hydrogenation reactions.

Also bed are methods for preparing alcohols from ketene and diketene via betabutyrolactone (BBL). Ketene is dimerized to form ne, diketene is hydrogenated to form BBL which is hydrogenated to form ls. In one embodiment, diketene is hydrogenated to form BBL which is hydrogenated to form butyric acid or a mixture of butanols, butyric acid and its esters. In one embodiment, diketene is hydrogenated to form a mixture of higher ls including three carbon and higher alcohols. In a variation of this embodiment, diketene is hydrogenated to form a mixture of higher alcohols and alkanes. In another ment diketene is reacted with an alcohol to form an acetoacetate ester which is hydrogenated to form butanol.

In one embodiment diketene is ted to methyl acetoacetate and reduced to form a butanol based product such as a mixture of 2-butanol and 1-butanol along with methanol. In one embodiment diketene is converted to butyl acetoacetate by reaction of butanol and diketene and reduced to form a butanol based product such as a mixture of 2-butanol and 1-butanol. In one embodiment diketene is converted to methyl acetoacetate and reduced in situ to form a butanol based product such as a mixture of 2-butanol,1-butanol and methanol.

In one embodiment ne is ted to butyl acetoacetate by reaction of butanol and diketene and reduced in situ to form a butanol based product such as a mixture of 2-butanol and 1-butanol. BBL may be made by the ion of diketene, by oxidation and ylation of propylene or by reaction of acetaldehyde with . In one embodiment the reduction of diketene to BBL and then to butyric acid is done with Raney nickel.

In one embodiment the reduction of diketene to BBL and then to butanol is done with a Copper Zinc catalyst commercially available from Johnson Matthey called the CZ29/2T catalyst.

In one embodiment the reduction of diketene to BBL and then to l is done with Ni/alumina catalyst. In one embodiment, the reduction of the diketene is done at a ature between 50 and 350 oC in the ce of a catalyst. In one embodiment the reduction of diketene is done with a copper zinc catalyst commercially available from Johnson Matthey called the CZ29/2T catalyst. Hydrogen pressures required for reduction of ne maybe from 10 psi to 1600 psi. In one embodiment the reduction of diketene is done at a re range of 200 to 500 psi.

In one embodiment the reduction of BBL to butanols is done with a Copper Zinc catalyst commercially available from Johnson Matthey called the T catalyst. In another aspect, the reduction BBL to butanols is done with Ni/alumina catalyst. In another aspect, the reduction of BBL is done at a ature between 50 and 350 oC in the presence of a catalyst. Hydrogen pressures required for reduction of BBL maybe from 10 psi to 1600 psi. In one ment the reduction of BBL is done at a pressure range of 200 to 500 psi or more preferably 300 to 500psi.

In one ment, the ketene produced is dimerized to produce diketene which can be converted to dehydroacetic acid (DHAA) in situ and hydrogenated to form higher alcohols and hydrocarbons. In one variation, methanol is used as a source of hydrogen using a copper based catalyst, such as a copper chromite based catalyst. In another aspect, diketene is converted to DHAA in a separate process step which is then reduced to form a ol product, which may be purified to a fuel grade composition. In another aspect, the alcohol mixture product synthesized from diketene starting material is dehydrated to yield a mixture of unsaturated hydrocarbons which is in turn hydrogenated to produce a mixture of hydrocarbons. In another aspect, DHAA is hydrogenated in the presence of a catalyst to form a mixture of alcohols and hydrocarbons. In one aspect of the above, the fuel composition is a mixture of ketones, alcohols and alkanes. In one variation of the above, the relative ratios of the ketones, alcohols and alkanes may be adjusted by varying the temperature of the hydrogenation and/or dehydration reaction. In another aspect of the above, the reduction of 4-heptanone, the dehydration of the 4-heptanol and the reduction to form heptane are all performed over the same catalyst bed.

In another embodiment, the alcohol mixture product synthesized from reduction of DHAA is converted directly in a single s step to hydrocarbons. In one embodiment the reduction of DHAA is done with a copper chromite, barium promoted catalyst O4, CuO, BaO, Graphite, CrO3, Cr2O3). In r aspect, the ion may be done by a copper zinc catalyst. An example of the later is commercially available from Johnson Matthey called the CZ29/2T st. In r aspect, the hydrogenation of DHAA may be done over a 2% ruthenium on alumina catalyst. In r aspect, the reduction of DHAA is done at a temperature between 50 and 350 oC in the presence of a st. Hydrogen pressures required for ion of DHAA may be from 10 psi to 1600 psi. In one ment, the reduction of DHAA is done at a pressure range of 200 to 500 psi. In another aspect, reduction of DHAA is done at 300 psi hydrogen pressure at 300 oC; or at 300 psi hydrogen pressure at 200 oC. In r embodiment DHAA can be hydrogenated to 4-heptanone, mixture of 4-heptanone and 4- ol or to 4-heptanol. In one embodiment, alcohols are dehydrated to yield a mixture of unsaturated hydrocarbons using gamma-alumina, ZSM-5 or like agents to form unsaturated hydrocarbon products which are in turn enated to produce a mixture of hydrocarbons.

Also described are methods to prepare ls, s and s. Ketene is dimerized to form diketene which is hydrogenated to form butyric acid. c acid is ketonized to produce 4-heptanone which is reduced to form anol which may be r converted to e, which can be used individually or as mixtures of compounds as fuels, ts and chemicals for industry. In another aspect, ketonization provides 4-heptanone with conversion of at least 85%, 95%, 98% or 99%. In another , the hydrogenation of the composition comprising 4-heptanone provides a mixture comprising butanol and 4-heptanol. In one aspect of the above, the hydrogenation of 4-heptanone provides a composition that is rich in 4-heptanol. In another aspect, the hydrogenation st, such as the hydrogenation of 4-heptanone, comprises a transition metal or a e of two or more transition . In another aspect, the catalyst is a copper chromite barium promoted catalyst, or a copper and zinc based catalyst. In one aspect of the above, the mixture comprising 4-heptanone, 4-heptanol, 3-heptene or isomers thereof and heptanes, or mixtures thereof, may be used as a fuel, or further blended with gasoline to form a blended fuel mixture. In one aspect of the above method, the linear and branched heptanes formed comprise of 1-heptene, 2-heptene, ene, 3-methylhexene, 3-methylhexene, 3- methylhexene, 3-methylhexene and es thereof. In another aspect, the zeolite is a ZSM-5 st. In another aspect of the method, the catalyst is a nickel on alumina catalyst. In another aspect of the above method, the reduction or hydrogenation, the dehydration, the hydrogenation and the isomerization steps are performed in a single reactor or on vessel using the same catalyst and catalyst bed, or mixture of catalyst and using the same catalyst bed.

In another embodiment butyric acid is ketonized to form a product containing 4- heptanone and some unreacted butyric acid which is hydrogenated to form 4-heptanol and butanol. This product may be used as a fuel, solvent or useful industrial chemical product directly or after purification into useful chemical products. In another aspect, diketene is reduced to form butyric acid which is converted to 4-heptanone. The 4-heptanone is reduced to form 4- heptanol. The 4-heptanol may be dehydrated and reduced to form heptanes. In another aspect, the 4-heptanone is hydrogenated to 4-heptanol, dehydrated to form heptenes and the heptenes reduced to form heptanes in the same reactor using a catalyst and hydrogen.

In another embodiment, butyric acid is synthesized from beta-butyrolactone which is sized from other starting materials such as propylene, acetaldehyde and , etc. In one embodiment, butyric acid is synthesized by carbonylation of n-propanol. In another embodiment, butyric acid is synthesized by carbonylation of n-propanol and n-propanol is obtained from the carbonylation and subsequent reduction of the propanoic acid t from l. In one aspect of the above, the alkyl compound is further purified to produce a fuel with a higher caloric value than ethanol.

In one embodiment, 4-heptanone is hydrogenated to 4-heptanol, 4-heptanol converted to heptanes and the heptanes formed isomerized to form a mixture of branched hydrocarbons. In a ion of the embodiment, the branched hydrocarbon rich product is used as a fuel. In another embodiment, the catalyst used in the reduction/dehydration/hydrogenation of 4-heptanone to form heptane is a copper/zinc oxide catalyst.

In one embodiment, ls are dehydrated to yield a mixture of unsaturated hydrocarbons which are in turn hydrogenated to produce a e of hydrocarbons. In r embodiment, alcohols are ated to yield a mixture of unsaturated hydrocarbons using gamma-alumina, ZSM-5 or like agents to form unsaturated hydrocarbon products which are in turn hydrogenated to produce a mixture of branched hydrocarbons. In another embodiment, alcohols are ated and reduced to form a product that ns straight chain saturated hydrocarbons that are isomerized over a zeolite catalyst to yield a mixture of branched arbons. In another embodiment, heptanol is dehydrated and reduced to form a product that contains straight chain hydrocarbons such as heptane that are reacted over a zeolite st such as ZSM-5 to yield a mixture of C14 hydrocarbons. In one embodiment the reduction of 4- heptanone is done with a copper chromite, barium promoted st (62-64% Cr2CuO4, 22-24% CuO, 6% BaO, 0-4% Graphite, 1% CrO3, 1% Cr2O3). In another aspect, the reduction of 4- heptanone may be done by a copper zinc catalyst. An example of the later is commercially available from Johnson Matthey called the CZ29/2T catalyst. Pressures required for reduction of 4-heptanone maybe from 10 psi to 1600 psi. In another aspect, the reduction of 4-heptanone is done at a re range of 200 to 500 psi. In r , the reduction of 4-heptanone is done at a temperature between 50 and 350 oC in the presence of a catalyst. In one aspect, the reaction is run at a ature between 175 and 350 oC. In one embodiment, reduction of 4- heptanone is done using hydrogen at 300 psi pressure and 300 oC or at 300 psi and 200 °C.

In one embodiment, butyric acid is reacted over a solid catalyst to form 4-heptanone. In a variation, butyric is reacted over gamma-alumina to form 4-heptanone. In another variation, the solid support is doped by a metal oxide. An example of this variation is a gamma-alumina catalyst doped with lanthanum oxide. In other embodiments, butyric acid is reacted over ceria, magnesia, hydrotalcites, zeolites and the like to form 4-heptanone.

In one embodiment 4-heptanone can be converted by means of hydrogenationdehydration step process over bifunctional Pt/Nb2O5 catalyst to linear heptanes. In another embodiment, anol can be dehydrated using a gamma-alumina catalyst to heptene, which can reduced in the presence of palladium catalyst to form hydrocarbons. In one ment, branched hydrocarbons can be obtained by dehydration-isomerization of 4-heptanol over a zeolite catalyst. In another embodiment 4-heptanone can be oligomerized in the presence of yst catalyst to produce a mixture of C14 unsaturated compounds which are converted to diesel fuel and jet fuel. In one aspect of the above method, the zeolite is a ZSM-5 catalyst. In another aspect, the above method provides a mixture of linear and branched arbons.

In one ment, 4-heptanol is prepared by synthesizing , dimerizing ketene to form diketene and hydrogenating ne to produce c acid. The butyric acid is ketonized by means of ceria-zirconia catalyst to form 4-heptanone which is reduced to heptanol. In another embodiment, the formed 4-heptanol above may be dehydrated to form a hydrocarbon fuel.

Also described are methods to prepare C5 and C6 alcohols and other products such as alkanes and ketones. In one embodiment ethanol is carbonylated to form propanoic acid which is dehydrated to form methylketene. Methylketene is dimerized and hydrogenated to form alcohol products. In one aspect, ethanol is converted to 2-methyl pentanol by the use of ketene and enation chemistry. Ethanol is carbonylated to form propanoic acid, the propanoic acid maybe dehydrated to form methyl ketene which is dimerized to form a methyl ketene dimer. The dimer of methyl ketene is hydrogenated to form 2-methyl pentanol. In another aspect, the alcohol product 2-methyl ol is dehydrated to yield a mixture of unsaturated hydrocarbons which are in turn hydrogenated to produce a mixture of hydrocarbons.

In one embodiment, l is carbonylated to form propanoic acid which is ketonized to form 3-pentanone. The anone is hydrogenated to form 3-pentanol. In one aspect, ethanol used in the s is manufactured from synthesis gas by carbonylation of ol and hydrogenation of the resulting acetic acid to form ethanol. In another embodiment, the ethanol used in the process is made from fermentation of , starches or biomass. Ethanol may also be manufactured from a cellulosic feedstock or from a petroleum feedstock.

Pressures required for enation ons may be from 10 psia to 1600 psia. In one aspect, the reduction is done at a pressure range of 200 to 500 psi. In another aspect, the reduction is done at a temperature n 50 and 350 oC in the presence of a catalyst. In another aspect, hydrogenation is done using hydrogen at 300 psi re and 300 oC or at 300 psi and 200 °C. In another embodiment 2-methylpentanol can be dehydrated by means of gamma-alumina catalyst to 2-methyl e which is reduced in the presence of a hydrogenation catalyst to form hydrocarbons.

In one embodiment, branched hydrocarbons for use as a gasoline component can be obtained by dehydration step of 2-methyl pentanol over a zeolite catalyst. In one embodiment, a method to synthesize a fuel includes the steps of carbonylation of ethanol to form propionic acid, the propionic acid is dehydrated to form methylketene, methyl ketene is dimerized to form a diketene analog. The diketene analog is further dimerized to form a tetraketene adduct, the tetraketene adduct is reduced to form C11 and C12 alcohols, the alcohols that can be dehydrated to form a fuel. In one aspect of the above process, the methyl ketene is prepared from propanoic acid. In another aspect, the propanoic acid is prepared by the carbonylation of ethanol. In one aspect of the above process, the l may be ed by a fermentation process, or by the hydrogenation of acetic acid. In another aspect, the catalyst used for the hydrogenation of (E) and (Z)ethylidenemethyloxetanone is a transition metal, or a mixture of two or more transition metals. In r , the catalyst is a copper and zinc based st or a copper chromite barium promoted catalyst. In another aspect of the above method, the method provides C6-7 ketones, ls, alkanes and es thereof. In another aspect, the ratio of the ketones, alcohols and alkanes may be varied by adjusting the temperatures of the hydrogenation reaction.

In a variation, there is described a method to prepare a fuel including the steps of carbonylating ethanol to form propanoic acid which is hydrogenated to form propanol and fed into the reaction mixture carbonylating ethanol to form a mixture of propanoic and butyric acids which are reduced to form a fuel mixture of propanol and butanol. In another , ethanol is homologated with carbon monoxide and en to form propanol, propanol is homologated with carbon monoxide and hydrogen to form butanol by g the propanol product from the first step back into the ethanol homologation mixture resulting in a product mixture of propanol and butanol which is used as a fuel. In another embodiment butanol can be obtained by the reductive carbonylation cascade of methanol to ethanol to propanol to butanol.

In one ion, the compounds may be synthesized by the steps outlined in figure 1, figure 2, figure 3, figure 4, figure 5, figure 6, figure 7, figure 8, figure 9, figure 10, figure 11, figure 12 or figure 13.

EXPERIMENTAL The following procedures may be employed for the preparation of the compounds of the present application. The starting materials and reagents used in preparing these compounds are either available from commercial suppliers such as SigmaAldrich, Alfa Aesar, etc or are prepared by s well known to a person of ordinary skill in the art, following procedures described in such references as Fieser and Fieser's Reagents for c Synthesis, vols. 1-17, John Wiley and Sons, New York, N.Y., 1991; Rodd's Chemistry of Carbon Compounds, vols. 1- and supps., Elsevier Science Publishers, 1989; Organic Reactions, vols. 1-40, John Wiley and Sons, New York, N.Y., 1991; March J.: Advanced Organic Chemistry, 4th ed., John Wiley and Sons, New York, N.Y.; and Larock: Comprehensive Organic Transformations, VCH Publishers, New York, 1989. rd organic chemical reactions can be achieved by using a number of different reagents, for example, as described in Larock: Comprehensive Organic Transformations, VCH Publishers, New York, 1989.

Samples were analyzed on a Agilent 6890 5973 GCMS system equipped with a JW1 DB624 column with dimensions of 30m x 250μ x 1.4μ. The method ran at 1ml/min flow, with oven temperature at 40 oC for the first two minutes followed by temperature ramp at 10 oC /min to a temperature of 240 oC which was held for 10 minutes. The solvent delay was set at 5 minutes. Chemical identities of compounds were confirmed by mass spectroscopic qualitative analysis on GCMS against a NIST 2011 library as well as by comparison of retention time t commercial standards. Analysis of samples with volatile alcohols was done on a Gowmac GC system using a Hayesep Q column with He and nitrogen carrier gases. Column ature was 180 oC, detector temp. was 150 oC, injector temperature was 150 oC, sample valve ature was 105oC detector current was 107mA and ion volume was 1 microliter. Gas samples were analyzed on Varian GC instruments. onally, some product mixtures were analyzed for presence of lower alcohols by tizing the alcohol mixture by dissolving in methylene chloride, adding excess of diisopropylethylamine (DIEA), dimethylamino pyridine (DMAP) and acetyl de or acetic anhydride. After standing for 30 minutes the reaction mixture was analyzed by GCMS. An experiment for lower molecular weight alcohol analysis was done as follows: The liquid product (30 μl) of the reaction was ved in 1 ml of methylene chloride, DIEA was added with a 10 μl syringe in ents until the medium was basic, 2 mg of DMAP was added followed by acetyl chloride. The solution was allowed to stand for about a half hour until the alcohols were esterified to their acetyl derivatives. The resulting e was analyzed on the GCMS giving a mixture with ethyl acetate, isopropyl acetate, butyl acetate and sec-butyl acetate. These values represented the approximate percentages of ethyl, isopropyl, butyl alcohols in a sample.

Some tables below show a theoretical estimate of calorific values of a mixture shown. is used calorific values published in literature available on the NIST website at www.nist.gov. For calorific values of molecules like 2-heptanol and 4-heptanol that were not readily available (an isomer’s heat of combustion) like the 1-heptanol isomer’s calorific value was used in calculations. The quality of GCMS NIST library matches are listed on the last column of tables. Apparatus used for hydrogenation reactions was fabricated in house using standard pipes and parts and instruments available from companies such as ok, Omega engineering, etc. Glassware was purchased commercially or fabricated.

Diketene is manufactured on an industrial scale by the dehydration of acetic acid to ketene. It can be synthesized from various other starting materials including acetic anhydride, acetone, acetyl halides, etc. Ketene was generated by thermal decomposition of acetone and dimerized to diketene at low temperature. DHAA is manufactured on commercial scale from diketene and is commercially available.

Experiment 1: Synthesis of diketene: The r system (Fig. 15) was installed inside of a good working fume hood. The feed stream of acetone vapor was generated by passing argon through a glass bubbler filled up with acetone which was then passed to the top of a vertical hollow quartz tube with length of 47 cm and internal diameter of 22 mm. At the lower part of the quartz tube (5 cm from the bottom) was placed the removable silica foam monolith disk with 45 pores per inch, 20 mm diameter and 0.1 cm ess. The disk was ted inside of the reactor by a built-in quartz frit and temperature of the disk was ed with an external thermocouple placed in a glass pocket located under the frit. The quartz tube was placed in a cylindrical e where the ature was controlled with a PID controller. The ketene from the quartz tube was passed through a condenser cooled with cold water (bearing a graduated cylinder attached at the bottom receiver for liquid sate) followed by three cylindrical gas traps connected in series filled with acetone and immersed in a dry ice/acetone baths. At the end of the line was installed the fourth glass trap filled up with acetone kept at room temperature with the outlet tube placed into the hood’s exhausting vent.

The bubbler and three glass cylinder traps were charged with 300 ml of dry e (99.5%) each and the traps were immersed in a dry etone bath at a temperature of minus 72 oC. The fourth glass trap was charged with 150 ml of acetone at room temperature. The condenser was connected to ating cold water (8 – 12 oC) from a te water/ice bath.

The furnace temperature was set to 620 oC and argon was passed through the bubbler with acetone at a flow rate 0.7 - 1.0 l/min to deliver e vapour to the quartz tube reactor.

Temperature of acetone in the bubbler was maintained by a water bath at about 40 oC. The furnace temperature was kept at range of 620 - 670 oC to maintain temperature of the silica foam disk in the reactor at 470 – 510 oC. After 4 hours of the continuous passing of acetone stream vapour through the quartz reactor the furnace was turned off and the argon flow was d to 0.1 l/min. When the quartz tube reached room temperature the argon flow was stopped and the r system including three glass cylinder traps immersed in a dry ice/acetone bath was left to stand overnight. The acetone solutions from the three traps were collected and the solvent was evaporated under vacuum at a temperature range of 25 - 30 oC. The resulting dark red concentrate was distilled under vacuum at 55 – 70 oC using a cold finger (cooled with acetone/dry ice) and the formed white solid was melted into a separate flask to give a ish liquid weighing 16.5 g, including 75% of diketene, 16% of acetic anhydride and 5% of acetic acid. The diketene was taken forward into the next step without further purification.

Reduction of ne: Experiment 2: Reduction of diketene 62 hour (batch reactor): The reduction reaction was performed in a hydrogenation reactor consisting of a ½” er stainless steel tube fitted with a ball valve at the bottom and a cross (Swagelok parts) on the top. A thermocouple (top arm), side arms bearing a pressure gauge and pressure relief valve and a ball valve were attached to three arms of the cross and the fourth (bottom) arm was attached to the top of the stainless steel tube.

The tube was wrapped with heating rope and insulation was wrapped around the heating rope.

The ball valve on the bottom of the reactor is connected to a 3” length of 1/8” tube immersed in a cold water bath is connected to a 1/16” tube bearing a ball valve and needle valve to collect liquid samples from the reactor.

Procedure: 10.5 g of copper/zinc st CZ 29/2T (Johnson y) was weighed and loaded into the hydrogenation reactor. A 5% hydrogen in argon mixture was passed over the catalyst bed at 0.8 lit/min at a temperature of 180 oC for about 18 hours to reduce the catalyst.

The heating was shut off and the catalyst allowed to cool. The st was removed from the reactor under an argon atmosphere in a glove bag and placed in a porcelain dish and 0.7 ml of diketene was added dropwise to the catalyst pellets. The wetted catalyst pellets were poured back into the reactor, the reactor was sealed, removed from the glove bag and purged with argon and hydrogen three times each and then hydrogen filled to a pressure of about 1100 psi. Heating was started and temperature of the catalyst bed was about 209 oC. The hydrogenation was continued for about 62 hours after which the reactor was cooled and a sample of liquid collected from the reactor bottom. GCMS is of the sample showed the formation of higher alcohols including 1-butanol, 2-butanol, 2-pentanol, hexanol isomers, methyl cyclohexanol, heptanol isomers, etc in the reaction. GCMS qualitative analysis of higher alcohols formed is shown in Table 1 also presents a theoretical estimation of the calorific value of a mixture. s the major alcohol peaks in the GCMS, peaks were also observed indicating formation of esters, hydrocarbons and other oxygenated carbon compounds.

NIST Ret. Area Mol. ∆c liq. Normlzd Wt. ∆c liq. Energy/ Compound liq.

Min % Wt. kJ/gm Wt. Fraction kJ/Kg comp kJ/m 2-Butanol 5.6 6.5 74 35.9 481 7.6 35946 17290000 2660 1-Butanol 6.9 8.2 74 36.1 606.8 9.6 36081 21894000 2670 2-Pentanol 7.5 15.8 88 37.8 1390.4 22.0 37841 52614000 3330 2-Hexanol 8.7 2.2 102 39.1 224.4 3.5 39059 8764800 3984 l 11 1.37 102 39.1 139.74 2.2 39059 5458080 3984 4-heptanol 11.2 4.4 116 40.0 510.4 8.1 39974 20402800 4637 2-heptanol 11.5 4.3 116 40.0 498.8 7.9 39974 19939100 4637 3-methyl cyclohexano 12.5 17.7 116 40.0 2053.2 32.5 39974 00 4637 2,6-dimethyl - 4-heptanol 13.2 2.9 144 41.3 417.6 6.6 41292 17243400 5946 Total 6322.34 100.0 349200 2.46E+08 Average Energy/Kg of fuel 38859.2 Table 1. Products in 62 hr diketene reduction with an energy tion of the mixture.

Experiment 3: Diketene reduction 1 day: 10 g of copper/zinc catalyst pellets T (Johnson Matthey) was loaded into a ess steel tube, fixed bed enation reactor (described above) and reduced overnight in a stream of 5:95 hydrogen:argon at 180 oC. After 18 hours the catalyst was cooled to room temperature and poured into a flat porcelain dish in a glove bag under argon. 1gm of diketene was added dropwise to the catalyst pellets to wet them as evenly as possible. The reactor was ed, removed from the glovebag, purged thrice with argon, twice with hydrogen and then filled with hydrogen to 1100 psi. Temperature was raised to 67 oC and allowed to stand for 4 hours. A gas sample was taken for CO 2 and CO analysis indicating 2.55% CO and 0.5% CO2. Heating was shut off and the reactor was allowed to stand at room temperature overnight. Next morning, g was resumed and ature was raised to 210 oC. The reaction absorbed hydrogen with pressure dropping from 1200 psi to 940 psi so hydrogen was filled as required to keep pressure in the range of 1045 to 1240 psi. After 4.5 hours of heating at 210 oC a liquid sample was taken by cooling the sampling port with ice water bath and the heating was shut off. GCMS qualitative analysis of higher alcohols formed is shown in Table 2 and also presents a theoretical estimation of the calorific value of a mixture. Mixture of products indicated complete conversion of diketene, 48% by area of higher alcohols formed of which 9.4% were 1-butanol and nol combined.

GC ∆c NIST Area Mol. ∆c liq. Normlzd Wt. Energy/c Compoun d Ret. liq. ∆c liq.

% Wt. kJ/gm Wt. Fract. omp Min. kJ/Kg kJ/mol 2-Butanol 5.6 5 74 35.9 370 7.6 35946 13300000 2660 1-Butanol 6.9 4.4 74 36.1 325.6 6.6 36081 11748000 2670 2-Pentanol 7.5 11.9 88 37.8 1047.2 21.4 37841 39627000 3330 nol 8.7 3.7 102 39.1 377.4 7.7 39059 14740800 3984 Hexanol 11 0.54 102 39.1 55.08 1.1 39059 2151360 3984 4-heptanol 11.2 3.14 116 40.0 364.24 7.4 39974 14560180 4637 2-heptanol 11.5 2.6 116 40.0 301.6 6.2 39974 00 4637 3-methyl cyclohexan ol 12.5 12.4 116 40.0 1438.4 29.4 39974 57498800 4637 2,6- dimethyl 4- heptanol 13.2 4.3 144 41.3 619.2 12.6 41292 25567800 5946 Total 4898.72 100.0 349200 191250140 Average Energy/Kg of fuel 39040.8392 Table 2. Products in 4.5 hr diketene reduction mixture with an energy estimation of the same.

Experiment 4: Diketene reduction 30 minutes: 8.44 g of a -zinc oxide based catalyst Pricat CZ29/2T (Johnson Matthey) was placed in the enation reactor and purged with argon thrice followed by a stream of 5% H2/argon at 1l/min ght. The temperature of the reactor yst bed) was in the 170 to 210 oC range during the reduction. The 5% hydrogen in argon was replaced by a stream of pure hydrogen at 0.4 l/min at a temperature of 160 to 180 oC for 40 s. Heating was stopped and the reactor cooled down with the 5% hydrogen stream. The reactor was placed in a glove bag under argon and catalyst removed and carefully wetted dropwise with 1 ml of diketene. The catalyst wetted with the diketene was then placed back in the r and the reactor sealed, removed from the glove bag and purged thrice with argon. en pressure was set to 1100 psi and heating was started. The temperature rose rapidly from room ature to around 188 oC as hydrogen was absorbed by the reaction.

Heating was switched off about 30 minutes after temperature was reached. The pressure was between 1180 to 930 psi. The reactor vapors were condensed into a liquid using an ice water bath, collected and sampled on the GCMS. GCMS analysis of the sample showed the formation of higher alcohols including 1-butanol, nol, 2-pentanol, hexanols, heptanols and methyl cyclohexanol, etc in the reaction. GCMS qualitative analysis of higher alcohols formed is shown in Table 3, also presents a theoretical tion of the calorific value of a mixture. Besides the major alcohol peaks in the GCMS, peaks were also observed indicating formation of esters, hydrocarbons and other oxygenated carbon compounds. GCMS qualitative analysis of higher alcohols formed is shown in Table 3 and also presents a theoretical estimation of the calorific value of a mixture. te conversion of diketene was observed, 44% of higher alcohols of which 1-butanol and 2-butanol were 9%.

GC NIST Area Mol. ∆c liq. Normlzd Wt. ∆c liq. Energy/co Compound Ret. ∆c liq.

Percent Wt. kJ/gm Wt. Fract kJ/Kg mp Min. kJ/mol 2-Butanol 5.6 3.8 74 35.9 281.2 6.4 35946 10108000 2660 1-Butanol 6.9 4.8 74 36.1 355.2 8.1 36081 00 2670 2-Pentanol 7.6 11.3 88 37.8 994.4 22.5 37841 37629000 3330 2-Hexanol 8.8 0.93 102 39.1 94.86 2.2 39059 3705120 3984 Hexanol 11 0.4 102 39.1 40.8 0.9 39059 1593600 3984 4-heptanol 11.3 3.7 116 40.0 429.2 9.7 39974 17156900 4637 2-heptanol 11.5 2.2 116 40.0 255.2 5.8 39974 10201400 4637 3-methylcyclohexanol 12.6 16.9 116 40.0 1960.4 44.4 39974 78365300 4637 2,6-Dimethyl heptanol 13.3 144 41.3 41292 5946 Total 4411.26 100.0 349200 171575320 Average Energy/Kg of fuel 38894.8554 Table 3. ts in a 0.5 hr diketene reduction mixture with an energy estimation of the same.

Experiment 5: ne reductions in continuous flow reactor system on a copper-zinc catalyst: The hydrogenation was performed in a steel tube reactor (see fig 14) (made from ok parts, volume 16 ml) consisting of a ½” diameter stainless steel tube fitted with a ball valve at the bottom and a 1/4” union ess steel cross on the top. A thermocouple was ed to the top arm of the cross with one of the (cross) side arms bearing a pressure gauge, pressure relief valve and a ball valve. The other side arm of the ¼” union cross was connected to a 1/16” tube which was attached to a Gilson 307 HPLC pump. The 1/16” tube entered the reactor and extended down till it was just above the catalyst bed. The bottom arm of the cross was ed to the top of the ½” stainless steel tube. A second couple was installed in the middle section to measure internal temperature. The tube was wrapped with heating rope and insulation was wrapped around the heating rope. A third thermocouple was placed under the heating rope. All three thermocouples were connected to a digital display. The ball valve on the bottom of the reactor is ted to a coil of 1/8” stainless steel tube that was ted to 2” length of ¼ inch tube with a drain at its bottom for liquid condensate and a vent near its top that carried out non-condensing gases. This coiled tube and lower portion were cooled with ice water and served as a trap to t liquid. The end of the gas vent had a ball valve and the liquid collecting end had a needle valve so that it could be opened slowly to collect liquid samples. The gas outlet of the condenser, including a port for gas sampling was connected to a back pressure gauge that enabled control of reactor pressure which was in turn connected to a flow meter that vented reactor gases to the hood via a tube.

Procedure: 6.5 g of the CuO-ZnO catalyst (Unicat, LS-402, 5 x 2 mm) was placed in the reactor and covered on top with 1.0 g glass beads. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.4 l/min overnight with temperature of the reactor 190 -195 °C and then 5% H2/nitrogen was ed by a stream of pure en at 0.4 l/min at 195 °C for 1h. The r was initially heated to 210 oC, hydrogen pressure was set up to 300 psi at hydrogen flow rate of 0.3 l/min and HPLC pump was turned on to pump diketene (GC: 95.1% diketene, 3.5% acetic acid, 0.7% acetic anhydride) at a rate of 0.05 ml/min. The experiment was run for 2.3 h at temperature gradient from 210 to 230 oC (catalyst temp at middle of the reactor) and samples of the reaction mixture were collected for GS-MS analysis (in methyl acetate). GC analysis for volatile ts on a Gowmac GC against quantitative standards showed samples S3, S5, S8 contained about 31 to 32% isopropanol and about 4% ethanol each by volume. GCMS qualitative analysis of products formed is shown in Table 4, also an estimation of the calorific value of a sample e 2 (S2) based on the GCMS chromatogram is shown in Table 4a.

Reactor temp.,oC 205 217 224 224 209 Process time, min 59 79 99 119 139 (sample no.) (sample weight gms) (S2) (S4) (S6) (S8) (S10) (0.33g) ) (0.43g) (0.40g) (0.54g) GCMS Area % 1.3 1.1 1.0 0.8 0.8 2-Butanone 2-Butanol 29.5 26.7 25.1 22.3 20.7 1-Butanol 42.9 46.2 43.9 39.8 37.2 2-Pentanol 2.1 1.8 1.7 1.8 1.7 Diketene 0.6 0.9 0.7 trace 0.4 Butyric acid i-propyl ester 2.5 2.6 9.7 5.3 5.7 anol 4.4 4.4 3.9 4.7 4.8 2-Heptanol 3.1 3.0 2.6 2.8 2.7 Butyric acid sec-butyl ester 0.9 0.9 1.1 1.4 1.4 3-Methyl cyclohexanol - 1.3 1.5 1.8 1.7 Butyric acid butyl ester 2.2 2.6 3.2 4.3 4.4 nol + 2-Butanol 72.4 72.9 69.0 62.1 57.9 Table 4 Products seen in a Cu-ZnO diketene hydrogenation GCMS analysis.

Samples showed over 99% of diketene was reacted, included 69-83% higher alcohols, of which 58-73% was 1-butanol and 2-butanol. The product e was also observed to contain esters and a ketone which combined with the alcohols was 82-94% of product. 35cm 93.: O vs cam » J S v ; “$.55 axe 9 % EN No.0 5:» >996 GvES 29:3 3.9 ordn :15 5:32 a, I'll % Elam. 9:333; 9:236 «8mm OcNLC Sr %III% lllll%%Ill lg E glam“. dug—mm c2293, 35,0 £2695 OF: m_5...,o.:< 355m 0x52 . 02% «v 52 3...er Comancfiuwu $3.3 3. 3.3m axis: .655 92.2 amt: “m2 glmuul axe finmwd axomvd .0 GIN m“)v‘I—v-F «- a J_<.._.O._.

Experiment 6: ne reductions in continuous flow r system on a nickel-alumina catalyst: 5.3 g of the NiO-Al2O3 catalyst (Unicat, NH-100, extruded) was placed in the reactor described in experiment 5 above and covered on top with 1.3 g glass beads. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.4 l/min overnight at temperature of the reactor at 190 °C and then 5% H2/nitrogen was replaced by a stream of pure hydrogen at 0.4 l/min at 190-195 °C for 2h. The reactor was initially heated to 193 oC, hydrogen pressure was set up to 300 psi at hydrogen flow rate of 0.3 l/min and HPLC pump was turned on to pump diketene (GC: 95.1% diketene, 3.5% acetic acid, 0.7% acetic anhydride) at a rate of 0.05 ml/min. The ment was run for 1.5h at temperature gradient from 195 to 240 oC yst temp at middle of the reactor) and samples of the reaction mixture were collected and analyzed by GC-MS analysis (in methyl acetate). GCMS qualitative is of products formed is shown in Table 5 and also a theoretical estimation of the calorific value of a sample mixture 3 (S3) is shown in Table 5a. 100% of diketene was reacted with product showing 41-51% higher alcohols of which 35-43% was 1-butanol and 2-butanol. The mixture was observed to also n other products including butyrate esters, acetic acid which along with higher alcohols were about 88%.

Reactor oC 225 232 237 242 213 Process time, min 48 58 68 80 93 (sample no.) (S1) (S2) (S3) (S4) (S5) Sample weight 0.48g 0.39g 0.32g 0.34g 0.10g GCMS Area % 2.7 1.7 2.0 2.0 1.3 2-Butanol Acetic acid 1.7 1.6 1.3 1.1 1.2 1-Butanol 40.2 37.8 37.6 38.3 33.4 2-Pentanol 1.9 1.2 1.1 1.0 0.9 Butyric acid i-propyl ester 1.2 1.1 1.2 1.3 0.7 Butyric acid 19.2 22.6 22.5 20.9 25.4 3-Hydroxybutyric acid methyl ester 1.7 1.9 1.6 1.1 1.1 4-Heptanol 3.4 2.8 2.7 2.6 3.0 2-Heptanol 2.4 2.0 2.0 1.9 2.0 Butyric acid butyl ester 13.4 15.0 16.4 18.2 19.0 nol + 2-Butanol 42.9 39.5 39.6 40.3 34.7 .355 9.52 9. R .n an E exox .252 3 {uomd 3mm,» S {ingum {www.m m,m~ 05.8 3290.; 3..wa 93,. m to u 3:23. 3.3m 9:22 omdm .. 32 ”5:9 .3.de 5. ‘ 53» Er m $299.. 35.6 6x3 mm mwd am an x o m 29:3 . xmhucm 933 9.me wmdm .513 9wmm “02 832:: (30m £3. w m.w~ 5:962 9:22 .cmaz. 3.26. 0:336 £28m? hrucm GEE. .uz I'll g. E:E:_m-_2 3299: 2.:qu 9:: £0355 >9ccu am 62 oEfiF EIIIIIIIIIIIIIIE%%HH Experiment 7: Diketene reductions in continuous flow reactor system on a Cu-Zn and nickelalumina catalyst: First 5.1 g of the CuO-ZnO catalyst (Unicat, LS-402, 5 x 2 mm) and then 1.97 g of the NiO-Al2O3 catalyst (Unicat, NH-100, extruded) was placed in the reactor described in experiment 5 above covered on top with 1.4 g glass beads were placed in the reactor. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.4 l/min overnight at temperature of the reactor at 230 – 240 °C and then 5% rogen was replaced by a stream of pure hydrogen at 0.4 l/min at 210 °C for 2h. The reactor was initially heated to 212 oC, hydrogen pressure was set up to 300 psi at hydrogen flow rate of 0.3 l/min and HPLC pump was turned on to pump diketene (GC: 91.6% diketene, 2.9% acetic acid, 3.9% acetic anhydride) at a rate of 0.05 . The experiment was run for 1.7h at temperature gradient from 190 to 220 oC (catalyst temp at middle of the reactor) and samples of the reaction mixture were collected and analyzed by GC-MS analysis (in methyl acetate). GCMS qualitative analysis of products formed is shown in Table 6 and also a theoretical estimation of the calorific value of a sample mixture 5 (S5) is shown in Table 6a. 100% of diketene was reacted, samples showed 91-96% of t included a e of higher alcohols, butyrate esters and acetic acid, higher ls were in 34-77% range of which 33-77% was 1-butanol and 2-butanol.

Reactor temp.,oC 197 194 190 189 195 Process time, min 60 70 80 90 101 (sample #) (S1) (S2) (S3) (S4) (S5) Sample weight 0.31g 0.36g 0.30g 0.24g 0.34g GCMS Area % 2-Butanol 11.5 1.7 1.3 1.5 1.0 Acetic acid 9.4 0.9 0.7 0.7 0.8 nol 65.8 56.5 49.0 42.4 32.3 2-Pentanol - - 0.3 - - Butyric acid methyl ester - 1.0 1.1 1.0 1.0 Butyric acid ethyl ester - 0.7 0.9 1.1 1.4 c acid i-propyl ester - 0.7 0.9 1.1 1.4 Butyric acid 4.7 11.5 13.9 14.3 17.1 3-Hydroxybutyric acid methyl ester 4.0 1.7 2.0 2.1 2.1 4-Heptanol - 0.7 0.6 0.5 0.5 Butyric acid butyl ester - 20.1 23.3 28.3 33.3 1-Butanol + 2-Butanol 77.3 58.2 50.3 43.9 33.3 Table 6. Products seen in GCMS samples of Cu-ZnO + Ni-alumina diketene reduction samples taken over time. 45.9w «53$ 3.5:» >905 95,: 222:. 923 35cm ex; .mz 5:26.: .23..» 2.33% K. EcEsELZ $0283 gaglllag + :320 %%IIIIII% $2.8 C:1.\.-:U 29:5 E ofiam 355. 95.2 3.: Bonsai #0 62 lfiégga .3 3; Bank COmEE—Cmv 3 332 EIIIIIIIIIIIHé! lllllllllllligééll ggggfiélllllliE%E%%E%E%IIIHggéggéggéllligéégééllllllliIlllllllllllliIIIIIIIIIIIIHIIIIIIIIIIIIHIIIIIIIIIIIIH IIIIIIIIIIIIH IIIIIIIIIIIIH IIIIIIIIIIIIH IIIIIIIIIIIIHIIIIIIIIIIIIH IIIIIIIIIIIIH IIIIIIIIIIIIHlllllllllllla g Experiment 8: Hydrogenation of beta-butyrolactone (BBL) with a Cu-Cr catalyst in a batch reactor: The reduction reaction was performed in a hydrogenation reactor consisting of a eter stainless steel tube fitted with a ball valve at the bottom and a cross on the top. A thermocouple, side arm g a pressure gauge and pressure relief valve and a ball valve were attached to three arms of the cross and the third arm was attached to the top of the stainless steel tube. The tube was wrapped with heating rope and insulation was wrapped around the heating rope. The ball valve on the bottom of the reactor is connected to a 3”length of 1/8” tube ed in a cold water bath which is connected to a 1/16” tube bearing a ball valve and needle valve to collect liquid samples from the reactor. Procedure: 15.3 g of the barium promoted copper chromite catalyst (Stream Chemicals, (62-64% Cr2CuO4, 22-24% CuO, 6% BaO) was placed in the hydrogenation reactor and purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.2 l/min overnight at temperature of the reactor 180 °C. The 5% H2/nitrogen was replaced by a stream of pure hydrogen at 0.2 l/min for 1h. The hydrogen stream was replaced with nitrogen and the reactor was cooled down to room temperature and under continuous en flow 0.50 ml of BBL was injected into the catalyst bed. The reactor was washed 3 times with hydrogen and then filled with hydrogen to a pressure of 600 psi. Heating was started and temperature of the catalyst bed was maintained at 180 – 190 °C and hydrogen pressure at 500- 700 psi for 3 h. The reactor was cooled down to room temperature, washed with nitrogen and the catalyst was removed and washed with 2 ml of methyl acetate. The wash was filtered and directly ed by GC-MS. Similar experiments were performed using CuO/ZnO, Ni/alumina and Ru/alumina catalysts. The obtained results are summarized in Table 7.

GC/MS: area % 1 Catalyst Conditions 1-Butanol 2-Butanol ∑ ∑ Butanols tes 2) Cu chromite 180o-190oC, 500-700psi, 3h 47.1 2.6 49.7 17.4 -65%ZnO 180o-190oC, 600-700psi, 3h 37.4 20.7 58.1 8.8 50%NiO/ alumina 00oC, 600-760psi, 5h 33.2 16.7 49.9 14.4 lumina 180o-195oC, 0psi, 4h 4.7 5.0 9.7 21.2 1 Peaks related to the solvent component (ethyl acetate and acetic acid) are excluded. 2 Butyrates include butyric acid and its , esters of 3-hydroxybutyric acid and 1,3-butanediol.

Table 7 Products from GCMS analysis of BBL hydrogenation Continuous Flow Reactor ments BBL: Experiment 9: Hydrogenation of BBL with a Ni-alumina catalyst: Continuous flow reactor setup: The reduction reaction was performed in a steel tube reactor (made from ok parts) consisting of a ½” er stainless steel tube fitted with a ball valve at the bottom and a 1/4” union stainless steel cross on the top. A thermocouple was attached to the top arm of the cross with one of the (cross) side arms bearing a pressure gauge, pressure relief valve and a ball valve. The other side arm of the ¼” union cross was connected to a 1/16” tube which was attached to a Gilson 307 HPLC pump. The 1/16” tube d the r and extended down till it was just above the catalyst bed. The bottom arm of the cross was attached to the top of the ½” stainless steel tube. The tube was wrapped with heating rope and insulation was wrapped around the heating rope. Another thermocouple was placed under the heating rope. Both the thermocouples were connected to a digital display. The ball valve on the bottom of the reactor is ted to a coil of 1/8” stainless steel tube that was connected to 2” length of ¼ inch tube with a drain at its bottom for liquid condensate and a vent near its top that carried out noncondensing gases. This coiled tube and lower portion are cooled with ice water and served as a trap to collect liquid. The end of the gas vent had a ball valve and the liquid ting end had a needle valve so that it could be opened slowly to collect liquid samples. ure: 7.0 g of the NiO/alumina catalyst t, 50%NiO/Al2O3) was placed in the reactor and covered on top with 0.9 g glass beads. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.3 l/min overnight at temperature of the reactor 180 °C and then 5% H2/nitrogen was replaced by a stream of pure hydrogen at 0.3 l/min for 1h. The reactor was initially heated to 260 oC, hydrogen re was set up to 300 psi at hydrogen flow rate of 0.40 l/min, HPLC pump was turned on and BBL was pumped at a rate of 0.04 ml/min. The experiment was run for 6 h at temperature gradient from 260 to 170 oC and samples of the reaction mixture were collected and ed by GC-MS analysis (in methyl acetate). The obtained results are summarized in the Table 8.

Sample No. S2 S3 S4 S6 S7 S8 S9 S10 S11 S12 S13 S15 S16 S17 Reactor 260 259 259 254 251 257 253 242 196 180 180 185 187 174 temp., oC Process time, 60 75 100 140 165 190 205 220 230 245 255 305 325 355 Sample wt. .13g .21g .31g .24g .41g .40g .27g .24g .17g .22g .10g .20g .65g .85g gms.

GCMS Area 77.7 85.1 81.7 87.8 69.4 5.7 8.8 9.4 9.0 13.4 21.2 2.3 0.4 1.2 Acetic acid 1-Butanol - - - - 19.1 74.4 86.8 87.3 88.0 83.7 74.3 40.5 13.9 4.7 Butyric acid - - - - - - - - - - - 44.1 80.0 90.7 Butyl - - - - - - - - - - - 10.5 3.7 1.9 butyrate BBL - - - - - - - - - - - - - - Table 8 ts in GCMS analysis of Ni-alumina BBL hydrogenation taken over time.

Experiment 10: Hydrogenation of BBL with a Ni-alumina catalyst at around 250 oC: 9.5 g of the NiO/alumina st (Unicat, 50%NiO/Al2O3) was placed in the reactor described in experiment above and covered on top with 1.2 g glass beads. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.3 l/min overnight at temperature of the reactor 180 °C and then 5% H 2/nitrogen was replaced by a stream of pure hydrogen at 0.3 l/min for 1h. The reactor was initially heated to 250 oC, hydrogen pressure was set up to 400 psi at hydrogen flow rate of 0.40 l/min, HPLC pump was turned on and BBL was pumped at a rate of 0.03 - 0.04 ml/min. The experiment was run for 6.7 h at temperature gradient from 250 to 180 oC and samples of the reaction mixture were collected and analyzed by GC-MS analysis (in methyl acetate). The obtained results are summarized in the Table 9.

Reactor temp., oC 254 256 225 228 227 227 225 252 254 180 Process time, min 165 195 220 245 265 285 305 330 350 400 BBL flow, ml/min 0.03 0.03 0.03 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Sample no. S3 S4 S5 S7 S8 S9 S10 S11 S12 S15 Sample wt. gms .24g .35g .17g .15g .44g .45g .35g .73g .74g .14g GCMS Area % Acetic acid 35.7 31.6 26.0 14.8 1.5 0.9 - 0.9 0.2 - 1-Butanol 16.5 25.1 43.8 66.4 66.6 61.9 57.2 33.8 30.6 26.6 2-Butanol 30.9 29.9 20.5 11.6 1.6 0.9 0.9 0.4 0.5 - ∑ Butanols 47.4 55.0 64.3 78.0 68.2 62.8 58.1 34.2 31.1 26.6 Butyric acid - - - - - 7.7 17.5 47.6 49.1 54.3 Butyl buytyrate - trace trace - 20.9 22.3 19.8 13.7 14.7 13.8 BBL 1.6 trace trace - - - - - - Table 9 ts seen in GCMS of products from Ni-alumina hydrogenation of BBL over time.

Experiment 11: Hydrogenation of BBL with a Ni-alumina catalyst as temperature was : 7.25 g of the umina catalyst (Unicat, 50%NiO/Al2O3) was placed in the reactor and d on top with 2.5 g glass beads. The reactor was purged with nitrogen followed by a stream of 5% H2/nitrogen at 0.3 l/min overnight at temperature of the reactor 180 °C and then 5% rogen was replaced by a stream of pure hydrogen at 0.3 l/min for 1h. The reactor was initially heated to 220 oC, hydrogen pressure was set up to 300 psi at hydrogen flow rate of 0.40 l/min, HPLC pump was turned on and BBL was pumped at a rate of 0.05 ml/min. The experiment was run for 6.5 h at temperature gradient from 220 to 200o to 240 oC and samples of the reaction mixture were collected and analyzed by GC-MS analysis (in methyl acetate). The obtained s are summarized in the Table 10.

Reactor temp., oC 221 224 224 224 199 201 201 233 247 232 224 239 Process time, min 112 127 147 182 222 247 287 327 340 352 368 389 Sample no. S2 S3 S4 S5 S7 S8 S9 S10 S11 S12 S13 S14 Sample wt. gms .03 .32g .43g 1.01g .58g .83g 1.56g 1.77g 1.05g ,43g .55g GCMS Area % 1-Butanol 56.6 69.0 70.9 49.1 26.5 13.4 6.9 3.3 2.6 3.5 3.7 2.5 2-Butanol 10.6 3.1 1.4 - 0.5 - - - - - - - ∑ Butanols 67.2 72.1 72.3 49.1 27.0 13.4 6.9 3.3 2.6 3.5 3.7 2.5 c acid - - - 30.1 61.4 78.7 77.6 93.8 94.2 91.4 91.0 92.

Butyl buytyrate - 13.8 17.4 15.1 8.5 4.7 2.3 1.3 1.5 2.6 3.4 2.6 BBL 4.3 1.9 0.6 0.5 - - - - - - - - Table 10. Products seen in GCMS analysis of BBL Ni-alumina hydrogenation over time.

% - GCMS area percent; the peak related to the t component, ethyl acetate was ed.

Reduction of Methyl Acetoacetate (MAA) Experiments: Experiment 12: Hydrogenation of MAA with a copper-zinc catalyst; Continuous flow reactor set up: The reduction reaction was performed in a hydrogenation r (made from Swagelok parts using the required unions, port connectors, reducers and valves as needed) consisting of a 1” diameter stainless steel tube reactor chamber that held catalyst. The reactor tube was wrapped in heat tape and insulation surrounded the heating tape. Five thermocouples were d to the reactor to monitor catalyst bed atures along the length of the reactor catalyst bed. The thermocouples were connected to a digital display. The top of the reactor was connected to a T-union one side arm of the union was connected to a 1/16” tube that was connected to a waters HPLC pump. The intake of the pump was dipped in MAA contained in a 50ml measuring cylinder. The other arm of the T-union on the top of the reactor was ted to a pressure ucer, hydrogen supply and a differential pressure gauge to adjust pressure and flow rate. The bottom end of the reactor was connected to a liquid condenser cooled by circulating ice water by a ¼” stainless steel tube. The condenser had a ball valve at its bottom to open and collect liquid samples. The gas outlet of the condenser was connected to a back pressure gauge that enabled control of reactor pressure which was in turn connected to a flow meter that vented reactor gases to the hood via a tube. Procedure: 95 g of copper/zinc oxide catalyst from Unicat 2) was loaded into the reactor and reduced overnight at 180 to 190 oC over a stream of 5% hydrogen 95% nitrogen flowing at about 500ml/min. Next morning, the en/hydrogen mixture was ed by hydrogen and reduction continued for another 2 hours. Hydrogen flow rate was set to around 500 ml/min and the catalyst bed temperatures were at 200, 261 and 251 oC for up, middle and bottom reactor zones respectively. 50 ml of MAA (purchased from Alfa Aesar) was poured into the HPLC pump reservoir, the pump purged for air s and flow commenced onto the reactor catalyst bed at 0.7 ml/min. Liquid sample was taken after about 30 minutes had passed and taken at about 10 minute intervals. GCMS of the samples (Table 1) indicated 2-butanol and 1-butanol as major products. Samples were analyzed for lower boiling solvents on a Gowmac GC system indicating ethanol, e, isopropanol, 1- propanol, 2-butanol and nol were in ratios of 7.7: 0.6:18.9:0.7:45.1:26.9, respectively.

The obtained results are summarized in the Table 11. 100% MAA was converted. 84-91% of products included higher alcohols and r amounts of methyl butyrate, 82-89% was higher alcohols of which 71-79% was 1-butanol and 2-butanol.

Sample No.

S3 S4 S5 Time (minutes) 80 90 110 Reaction Temperatures oC T1 67 70 67 T2 119 120 116 T3 183 185 176 T4 272 270 265 T5 262 265 265 GCMS Area Percent 2-Butanol area 51.5 42.7 46.8 1-Butanol area 27.7 28.4 30.2 Methyl butyrate 2.0 2.4 2.5 3-Hexanol 1.8 2.4 1.8 4-Heptanol 1.9 2.0 2.0 2-Heptanol 1.2 1.4 1.3 Ocatanol isomer 1.4 1.4 1.2 4-Octanol 1.6 1.8 1.7 nol 1.5 1.7 1.7 Table 11: Products observed from GCMS analysis Cu-ZnO MAA hydrogenation.

Experiment 13: Hydrogenation of MAA with a copper-zinc catalyst as temperature was varied: To the reduced catalyst bed used in the experiment above heated to ature range of 193 to 218 oC, MAA was added via the HPLC pump at 0.7ml/min. Liquid sample was collected after 18 minutes after the start of the pump and samples were analyzed on GCMS. Temperature of the reactor rose after initial liquid input and was controlled by decreasing heating from the heat tape. The top of the r was cooled to around 115 °C and the bottom zone had a ature of around 245 oC. The obtained results of GCMS qualitative analysis are summarized in the Table 12. 100% of MAA was reacted. 84-89% of product included higher alcohols and methyl butyrate of which 79-86% was higher alcohols and 74-80% are 1-butanol and 2–butanol.

Sample No.

S3 S7 S9 S12 S14 Time (minutes) 35 60 80 184 232 Reaction Temperatures oC T1 63 61 61 63 71 T2 116 107 108 112 128 T3 179 159 155 167 183 T4 254 229 230 233 223 T5 254 249 249 248 226 GCMS Area Percent 2-Butanol 50.6 46.5 47.5 46.1 43.5 1-Butanol 29.4 30.1 28.1 29.8 30.8 Methyl butyrate 3.2 4.7 5.6 4.8 5.2 3-Hexanol 1.2 0.9 0.5 0.6 0.6 4-Heptanol 0.9 0.9 0.7 0.7 0.9 2-Heptanol 0.6 0.6 0.4 0.4 0.6 Ocatanol isomer 1.0 0.9 0.7 0.8 0.9 4-Octanol 1.2 1.0 0.8 0.8 0.9 3-Octanol 1.0 0.9 0.5 0.4 0.6 Table 12: Products seen in GCMS analysis of products from MAA Cu-ZnO below 250 C hydrogenation over time.

Experiment 14: Hydrogenation of MAA with a copper-zinc catalyst as temperature was varied near 200 °C. 11.9 g of the CuO-ZnO catalyst (Unicat, LS-402, 5 x 2 mm) was placed in the reactor and covered on top with 1.9 g glass beads. The reactor was purged with en ed by a stream of 5% H2/nitrogen at 0.4 l/min overnight at temperature of the reactor at 150 °C and then 5% H 2/nitrogen was replaced by a stream of pure hydrogen at 0.4 l/min at 200 °C for 2h. The reactor was initially heated to 204 oC, hydrogen pressure was set up to 300 psi at hydrogen flow rate of 0.4 l/min and HPLC pump was turned on to pump MAA Aesar, 99%) at a rate of 0.1 ml/min. The ment was run for 3.2 h at temperature nt from 190 to 200 oC and samples of the reaction mixture were collected for GS-MS analysis. GCMS qualitative analysis of higher alcohols formed is shown in Table 13 and also a theoretical estimation of the calorific value of a sample mixture 8 (S8) is shown in Table 13a. 100% of MAA was reacted. 81-89% of the t showed higher alcohols, ketones and butyric acid esters. 64-71% was higher ls of which 51-60% was 1-butanol and 2-butanol.

Reactor temp.,oC 188 189 189 190 194 194 Process time, min 65 86 105 125 145 165 (sample #) (S4) (S6) (S8) (S10) (S12) (S14) Sample weight gms 0.73 0.90 0.72 0.91 0.54 0.71 GCMS Area % none 2.6 2.4 2.2 2.4 2.5 2.6 2-Butanol 32.9 30.7 29.0 29.6 30.5 34.4 1-Butanol 26.1 23.4 22.9 22.4 22.6 25.4 2-Pentanone 1.7 1.3 1.2 1.1 1.5 1.3 2-Pentanol 3.8 3.9 3.8 3.7 3.7 4.0 Butyric acid methyl ester 3.1 2.5 2.3 2.8 2.8 3.5 Butyric acid ethyl ester 4.7 5.3 5.4 5.3 5.3 4.6 Butyric acid i-propyl ester 1.2 1.0 1.0 1.0 1.0 - 4-Heptanone 1.0 1.0 1.1 1.0 1.0 - 4-Heptanol 4.3 4.4 4.4 4.3 4.2 3.6 2-Heptanol 2.7 3.0 3.1 2.8 2.7 2.4 Butyric acid sec-butyl ester 1.7 1.6 1.7 1.8 1.7 1.9 3-Methyl cyclohexanol 1.4 1.3 1.5 1.2 1.2 1.1 Butyric acid butyl ester 1.6 1.6 1.7 1.7 1.7 1.6 1-Butanol + 2-Butanol 59.0 54.1 51.9 52.0 53.1 59.8 Table 13. ts seen in GCMS of product samples from Cu-ZnO below 200 °C hydrogenation of MAA. 52 83cm 62 E%%|%%% II IIIIIIIIIIII $8.9 $8.3 $on 832:: :268 32.3. llllllllaolé 3.? IIIIll Haglnig 353323: lllglgfi- Il|%%%H% %%%%%%H% Illaaéllllllfl IIIIIIIIIIIIIIII llllllllllllll!‘ IIIIIIIIIIIIIIH IIIIIIIIH IIIIIIllllnlllllili IIIIIIIIIIIIIIH IIIIIIIIIIIIIIHIIIIIIIIIIIIIIH IIIIIIIIH TESFCO v... .uEmm 2953 2: .32. 20:95..

U 29:35.3 . com Erma; 3ch U252 32 mo; $.93“ $.55 is... $va 0.15.5— >223 .bz % % 2:3 Ema 3S9 $3.2 O:N-:U $8.3 .8 H8 . 3.2.99; o. mEUO 303.55 .3 . .5... 52 <0 lllll' gluig 921. 2 .r n HaIIgallli Illli Ill! lllll'llH IIIIIII'fi 459 Reduction of Dehydroacetic Acid (DHAA): Experiment 15: Hydrogenation of DHAA in dioxane solvent with a Ru-alumina catalyst: Batch reactor system setup: The ion reaction was med in a hydrogenation reactor (made from Swagelok parts) consisting of a ½” diameter stainless steel tube fitted with a ball valve at the bottom and a cross on the top. A thermocouple attached to the top arm, the side arms bearing a pressure gauge and pressure relief valve and a ball valve were attached to three arms of the cross and the bottom arm was attached to the top of the stainless steel tube. The tube was d with heating rope and insulation was wrapped around the heating rope. The ball valve on the bottom of the r is connected to a 1/8” stainless steel tube that had provision for cooling and collecting liquid samples that could be collected via a ball valve connected to a needle valve. 0.41 g of DHAA was dissolved in 1.5 mL of hot dioxane (99.8%) and the resulting homogenic solution was immediately pipetted evenly over 4.62 g of 2% Ru-alumina catalyst pellets (Alfa-Aesar). The ing wetted catalyst was left to air for 30 minutes and then was poured into the reactor. The reactor was sealed and purged with argon and hydrogen three times each and then en was filled to a pressure of 1010 psi. Heating was started and temperature of the catalyst bed was maintained at about 200 oC (180 - 207 oC) for 2.5 hours. After 0.5 h the pressure in the reactor was dropped to 720 psi and was refilled with hydrogen to 1080 psi and it was 920 psi in the end of hydrogenation. The reactor was cooled down and a sample of liquid was collected from the reactor bottom and analyzed by GC/MS. The analysis indicated formation of compounds described in Table 1 below. Tables show an analysis of products using calorific values published from literature available on the National ute of Standards and Technology website at nist.gov. For calorific values of molecules like anol and anol that were not readily available an isomer’s heat of tion like the 1-heptanol isomer’s calorific value was used in calculations. The GCMS peaks were matched by agilent GCMS software to the NIST 2011 library of MS spectra. The quality of matches are listed on the last column of the table. The average energy of a fuel produced from the selected products of an experiment is on the last line of the tables. GCMS qualitative is of higher alcohols formed is shown in Table 14 and also presents a theoretical estimation of the fic value of a mixture. 100% of DHAA was reacted. 33% of product observed was higher alcohols and some ketones. 18% higher alcohols were formed of which 16% was heptanols.

GC GC NIST Lib.

Mol. liq. Normlzd Wt. ∆c liq. Energy/ Compound Ret. Area ∆c liq. Match Wt. kJ/g Wt. Fraction kJ/Kg comp Min. % kJ/mol Qual. 1-Butanol 7 0.9 74 36.1 66.6 1.8 36081 66.06367 2670 90 2-Pentanone 7.2 2.7 86 36.0 232.2 6.4 36035 230.0352 3099 2-Pentanol 0 0 88 37.8 0 0.0 37841 0 3330 78 4-Heptanone 10.9 11.6 114 35.3 1322.4 36.4 35333 1284.566 4028 78 4-heptanol 11.3 12.6 116 40.0 1461.6 40.2 39974 1606.263 4637 78 2-heptanol 11.5 3.7 116 40.0 429.2 11.8 39974 471.6803 4637 3-Methyl cyclohexanol 12.6 1.1 114 38.3 125.4 3.4 38263 131.9129 4362 83 Total 3637.4 100.0 263502 3790.521 Average Energy/Kg of fuel 37.90521 Table 14: Products in Ru cat. DHAA reduction at 180-207 oC mixture with an energy estimation of the same.

Experiment 16: Hydrogenation of DHAA with a Ru-alumina catalyst: In the stainless steel inset was put 3.20 g of 2% Ru-alumina catalyst (Afa-Aesar) and 0.51 g of DHAA and the inset was placed inside of the reactor. The reactor was sealed and purged with argon and hydrogen three times each and then hydrogen filled to a pressure of 1100 psi. Heating was d and temperature of the catalyst bed was maintained at 0 oC for 3.3 hours. The pressure drop related to hydrogen consumption was ed and in the end of hydrogenation it was 900 psi. The reactor was cooled down, purged with argon, the inset was removed and the catalyst was washed with 5 mL of methyl e. The resulting wash was ed and analyzed by GC/MS. GCMS qualitative analysis of ts formed is shown in Table 15 and also presents a theoretical estimation of the calorific value of a mixture. 100% DHAA reacted. 41% was a mixture of higher alcohols and ketones of which 27.7% was higher alcohols and 23.4% of that was heptanols.

GC GC NIST ∆c Lib.

Mol. liq. d Wt. ∆c liq. Energy/c Compound Ret. Area liq. Match Wt. kJ/ Wt. Fractn. kJ/Kg omp Min. % kJ/mol Qual. 1-Butanol 7 0 74 36.1 0 0.0 36081 0 2670 90 2-Pentanone 7.2 2.3 86 36.0 197.8 4.4 36035 97 3099 2-Pentanol 7.5 4.3 88 37.8 378.4 8.4 37841 316.6659 3330 78 4-Heptanone 10.8 10.8 114 35.3 1231.2 27.2 4042 962.0594 4028 78 4-heptanol 11.2 17.7 116 40.0 2053.2 45.4 39974 1815.094 4637 78 2-heptanol 11.4 5.7 116 40.0 661.2 14.6 39974 584.5217 4637 3-Methyl cyclohexanol 12.5 0 114 38.3 0 38263 0 4362 83 Total 4521.8 100.0 232210 3835.97 Average /Kg of fuel 38.3597 Table 15 Products in a Ru-alumina DHAA reduction at 200-220 °C, 3.3 hrs mixture sample with an energy estimation of the same.

Experiment 17: Hydrogenation of DHAA in dioxane over a copper-zinc catalyst: 8.5 g of Copper zinc catalyst tablets were loaded into the steel tube hydrogenation reactor. A stream of % hydrogen/95% argon was passed over the catalyst at 0.5 lit/min as the catalyst was heated at 175 oC. After reducing for about 18 hours overnight, the reactor was cooled and the catalyst was poured into a porcelain dish at room temperature under an argon atmosphere in a glove bag. 600 mg of DHAA was suspended in 1.2 ml of dioxane and heated with a heat gun. The hot dioxane was immediately added to the st beads to wet the beads, the DHAA began to fall out of solution as the catalyst cooled. The catalyst beads were poured back into the hydrogenation reactor and it was sealed and removed from the glove bag. The r was then purged thrice with argon, twice with hydrogen and then filled to 1000 psi. The reactor was heated with the temperature rising to 210 oC. Hydrogen was refilled as it was absorbed by the on and pressure varied between 900 and 1220 psi. After 2.5 hours an ice bath was placed to cool the liquid sampling tube, heating switched off and a liquid sample collected. GCMS of the sample indicated peaks for 4-heptanone, 4-heptanol, anol and 1-butanol in a ratio of 14.2:71.4:12.6:1.5 respectively. Other products like 2,6-dimethylheptanol, n-heptane and 2,6- dimethylheptane were observed as lesser ts.

All DHAA starting material was consumed. GCMS qualitative analysis of higher alcohols formed is shown in Table 16 and also ts a theoretical estimation of the calorific value of a mixture. 27% of products included higher alcohols, ketone and alkane products. 23% was higher alcohols of which 21% was heptanols.

GC GC Norm - NIST Lib.

Mol. liq. Wt. ∆c liq. Energy/c Compound Ret. Area lzed ∆c liq. Match Wt. kJ/ Fractn. kJ/Kg omp Min. % Wt. kJ/mol Qual. 2-Butanol 5.6 0 74 35.9 0 0.0 35946 0 2660 83% Heptane 6.5 0.4 100 48.2 40 48170 0 4817 91 1-Butanol 6.9 0.5 74 36.1 37 1.3 36081 45.300305 2670 90 Pentanol 7.5 0 88 37.8 0 0.0 37841 0 3330 78 Hexanol 8.7 0 102 39.1 0 0.0 39059 0 3984 90 2,6,- Dimethylheptane 9.2 0.4 128 47.9 51.2 47852 0 6125 80 4-Heptanone 10.9 3.6 102 39.0 367.2 12.5 39000 485.94503 4028 78 4-heptanol 11.3 18 116 40.0 2088 70.9 39974 2832.2362 4637 78 2-heptanol 11.5 3.3 116 40.0 382.8 13.0 39974 519.2433 4637 Heptanol isomer (methylcyclo hexanol) 12.5 0 114 38.3 0 0.0 38263 0 4362 83 2,6-Dimethyl- 4-heptanol 13.2 0.5 144 41.3 72 2.4 41292 100.88225 5946 74 hexanol 13.9 0.6 130 40.7 78 2.6 40723 107.78419 5294 Total 2947 100.0 443451 3983.6071 Average Energy MJ/Kg of fuel 39.83607 Table 16. Products in Cu-ZnO DHAA reduction mixture with an energy estimation of the same.

Experiment 18: Hydrogenation of DHAA over Cu-Cr for 3 hours: 13 g of a copper chromite barium promoted catalyst containing about 62-64% Cr2CuO4, 22-24% CuO, 6% BaO, 0-4% Graphite, 1% CrO3, was weighed and added to the hydrogenation reactor described above.

The reactor was sealed and a mixture of 5% hydrogen/95% en mixture was passed over the catalyst for about 18 hours at a temperature range of 155 to 180 oC. The nitrogen/hydrogen gas mixture was replaced by a hydrogen gas stream and ion was continued for r one hour at 180 oC. The heating was shut off and system allowed to cool to room temperature. 0.5 g of DHAA was suspended in 1.5 ml of methanol and 1.5 ml of isopropanol and warmed gently with a heat gun until a clear solution was formed. The solution was quickly added to the st bed and the reactor was sealed up. The reactor was pressurized with hydrogen at 1100 psi and was heated. Temperature rose to 271 oC and the pressure rose to 1170 psi. g was decreased and ature fell to 224 oC. H 2 pressure dropped to 970 psi over about one and half hour and was refilled to 1140 psi. After g for 3 hours the sampling tube was cooled, sample was taken and heating was shut off. GCMS of the sample indicated formation of anol and nheptane as major products in a ratio of 18.8:16.7 area percents respectively. Other alcohols such as 2-butanol, 1-butanol, 2-pentanol, etc and alkanes such as yl es, 2,6-dimethyl heptanes, etc were observed in lesser amounts. All starting material was consumed. GCMS qualitative analysis of higher ls formed is shown in Table 17 and also presents a theoretical estimation of the calorific value of a mixture. 100% of DHAA was reacted. 63% of product mixture was observed to contain higher alcohols and alkanes. 32% were higher ls of which 17% was heptanols.

GC GC Norma- NIST Lib.

Mol. ∆c liq. Wt. ∆c liq. Energy/ Compou n Ret. Area lzed ∆c liq. Match Wt. kJ/gm Fractn. kJ/Kg comp Min. % Wt. kJ/mol Qual. 2-Butanol 5.6 1 74 35.9 74 1.0 35946 36.85436 2660 83% Heptane 6.5 18.8 100 48.2 1880 26.0 48170 1254.705 4817 91 1-Butanol 6.9 1.7 74 36.1 125.8 1.7 36081 62.88794 2670 90 Pentanol 7.5 1.2 88 37.8 105.6 1.5 37841 55.36466 3330 78 3-methyl heptane 8 3.2 114 48.0 364.8 5.1 47965 242.4296 5468 94 2,6,- Dimethyl - heptane 9.2 5 128 47.9 640 8.9 47852 424.31 6125 80 4-me thyl- pentanol 8.7 5.9 102 39.1 601.8 8.3 39059 325.6706 3984 78 4-heptan o 11.3 16.7 116 40.0 1937.2 26.8 39974 1072.904 4637 78 2-heptan o 11.5 0 116 40.0 0 0.0 39974 0 4637 pent Diol 12.4 0 0 0.0 0 91 3-me thyl- heptanol 12.7 1.9 130 40.7 247 3.4 40723 139.3621 5294 72 3-me thyl- heptanol 12.78 1.6 130 40.7 208 2.9 40723 117.3576 5294 83 2,6- Dimethyl decane 13.7 4 170 47.6 680 9.4 47565 448.1268 8086 74 2,6,8- hyl - nonanol 17 1.9 186 42.7 353.4 4.9 42742 209.2801 7950 Total 7217.6 100.0 544614 4389.253 Average Energy MJ/Kg of fuel 43.89253 Table 17 DHAA reduction over Cu-Cr catalyst mixture with an energy estimation of the sample.

Continuous flow Reactions. Reaction systems used (shown in Fig. 17) consisted of an upper liquid reservoir designed to melt any solid DHAA. It was made of stainless steel and fitted with a pressure transducer at the top, a tube connection to a helium cylinder to apply re and l flow of liquid and a tube at the bottom for liquid flow to the reactor chamber below.

The reservoir was ed in a heat bath equipped with g oil, means for heating the bath and thermocouples to monitor the temperature. The reservoir bottom tube was a 0.02” ID tube connected to another tube leading into the steel pipe reactor equipped with four thermocouples along its length and a pressure transducer. The top of the reactor was connected to a common line ing liquid from the reservoir and hydrogen gas from the hydrogen supply line which had a mass flow controller and thermocouple. The bottom of the reactor was connected to a chilled condenser that condensed liquids that were drained under pressure, ted and analyzed. The uncondensed gases and vapors exited the condenser through a tube that was ed with a back pressure regulator that was used to maintain reactor system pressure.

Experiment 19: Hydrogenation of DHAA over a copper chromite catalyst: The hydrogenation reactor was filled with 297 g of copper chromite barium hydroxide catalyst and reduced with 5% hydrogen 95% nitrogen overnight at 195 oC. The reduction was ued by replacing the hydrogen/argon mixture with en for another two hours to ensure proper reduction. The reactor was heated to about 350 oC at the mid section of the reactor and hydrogen and DHAA flow started. Table 18 below describes some temperatures, pressure and flow rates for the reaction. Seven samples collected ng 151 g. Total DHAA feed was 297 g. Reaction ters and products seen in GCMS are shown in Tables 18 and 19 respectively. 100% of DHAA was hydrogenated. 53% of product was observed to contain higher alcohols, alkanes and ketones. 30% was hydrocarbons, 9% was higher alcohols of which 6% was heptanols. Samples were collected and analyzed by GCMS. Table 20 below describes compounds seen in the GCMS qualitative analysis and gives an tion of the calorific value of a product sample of the reaction.

Time Reactor He DHAA Flow H2 flow DHAA Temp. Temp. Temp pressure, pressure, rate, ml/min rate, Temp. Top, Mid , bottom, psi psi l/min oC oC oC oC 1:23 297 309 8 18 164 459 350 304 1:34 302 310 4 14 161 167 357 415 1:45 276 292 6 6 156 311 299 411 Run halted for hydrogen cylinder switch. 2:00 307 320 6 17 150 217 334 324 2:10 311 323 5.6 17.6 146 214 278 297 2:20 311 323 5.1 16.6 144 227 234 238 2:30 312 322 4.8 17 139 237 256 258 Table 18 Reaction conditions in DHAA Cu-Cr cat. continuous flow reduction reaction.

Calorific values of samples collected are 5MJ/kg, S3-9.8MJ/KG, 9MJ/KG, S6- 32.6MJ/KG.

Ret GCMS Compound Time,min Area % Heptane 6.51 16.46% 2-Pentanone 7.15 2.18% 2 Methylheptane 7.88 2.20% Nonane 10.59 4.45% 4-Heptanone 10.86 6.13% 4-Heptanol 11.23 6.06% 4-Methylnonane 11.78 4.91% 4-Nonanone 14.46 2.14% 4-Nonanol 14.76 2.90% 4-Methylundecane 15.18 2.84% 2,6,10-Trimethylpentadecane 16.04 2.42% 52.7% of sample is shown here Table 19. Products seen in GCMS samples of DHAA Cu-Cr cat. continuous flow reduction Run 2 sample #2.

Energy /K G 7 5 . 0 4 . 9 . 6 0 . 6 6 . 9 3 1 . 4 . 3 9 . 8 9 4 . 4 . 0 0 . 1 M J 0.00 0.00 0.00 0 0 0 14.33 6.75 6 6.72 2 3 0 0 0.00 0.00 0.00 0 0.00 0 4 4 L weighted Net T A G 4 1 3 6 2 3 0 0 9 0 5 T O Net Energy /K . 8 . 3 . 6 . 4 . 2 . 8 . 4 . 5 . 8 . 0 . 1 M J 0.00 0.00 0.00 2 8 7 3 3 8 43.65 45.61 4 4 44.85 4 3 4 4 4 7 7 4 0.00 0.00 0.00 5 4 0.00 0 4 4 t y w % % % % 9 % % % % % % % % b 0.00% 0.00% 0.00% 5 . 2 3 5 9 1 3 7 7 0 . 0 0 . 5 2 1 . 5 32.83% 14.80% . 9 4 0 1 14.99% 6 . 7 . 6 7 0 . 8 1 . 8 0.00% 0.00% 0.00% . 9 0 0.00% 0 . 0 1 0 ed Net G /K J M 0 7 y 0.00 0.00 0.00 0.00 0.00 0.00 0.52 0.15 0.00 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 . 0 .8 0 e rg n E o ls n e h P Net Energy G /K .1 7 M J 33.18 34.48 32.21 3 3 t w y % % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 1.56% 0.44% 0.00% 0.61% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 . 0 0 2 .6 2 weighted Net Energy G /K 0 1 J . 0 . 2 M 0.00 0.00 0.00 0.07 0.00 0.00 0.00 0.00 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 0 IS C G 1 M Net Energy J /K . 0 M 28.84 45.30 3 8 wt y % % % b 0.00% 0.00% 0.00% 0.25% 0.00% 0.00% 0.00% 0.00% 0.32% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 . 0 0 7 . 5 0 weighted Net Energy G /K . 0 0 .5 9 M J 0.00 0.00 0.00 0.00 0.25 0.16 2.99 0.96 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 4 s n e G 0 to /K J .9 8 K e Net Energy M 0.00 36.00 37.45 39.00 39.40 40.20 3 wt % 9 % % b y 0.00% 0.00% 0.00% 0.00% 0.70% 0.44% 7.67% 2.43% 0.55% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 0 . 0 . 7 1 1 weighted Net Energy /K G 0 . 0 8 .9 M J 0.00 0.00 0.00 0.00 0.00 0.00 0.27 0.32 2.36 2.61 2.02 1.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 8 s a tic G 5 m J /K 0.00 42.10 42.60 42.90 42.30 41.50 41.50 4 2 .1 A r o Net Energy M w t % % 0 % b y 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.64% 0.74% 5.50% 6.16% 4.87% 3.38% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 . 0 0 .3 1 G 8 weighted Net Energy /K 0.00 0.00 0.00 0.00 0.00 7.61 0 . 0 .2 M J 0.00 5.32 2.79 3.92 0.91 2.01 0.39 0.89 0.00 0.00 0.00 0.44 0.00 0 4 s n e G 7 lk a Net Energy /K J 0.00 48.17 47.60 47.80 47.70 47.60 47.50 47.40 47.50 45.89 . 7 7 A M 4 0.00% 0.00% 0.00% 0.00% 0.00% 15.79% 11.19% 5.84% 8.21% 1.91% 4.22% 0.83% 1.87% 0.00% 0.00% 0.00% 0.97% 0.00% % wt 4 % 0 . 0 0 % b y 0.00% 5 0 .8 0.00 0.00 0.00 0.69 0.43 2.94 0.00 1.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 G 0 . 0 0 weighted Net Energy /K 2 .2 M J 0.00 5 0.00 37.80 39.10 41.08 0.00 41.30 ls h o G 9 o J /K .4 0 A lc Net Energy M 4 0.00% 0.00% 0.00% 1.84% 1.11% 7.16% 0.00% 2.79% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% % t 9 % w . 0 0 y 0 . 8 2 1 % b 0.00% Table 20. GCMS data of DHAA Cu-Cr hydrogenation run2 sample 2 products with estimation of calorific value of the mixture 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 L 's 2 0 A O T f C 1 T # o Experiment 20: Hydrogenation of DHAA over a copper zinc catalyst: The reactor was filled with 544 g of copper zinc catalyst and reduced with 5% hydrogen 95% nitrogen overnight at 195 oC. The reduction was continued by replacing the hydrogen/argon mixture with hydrogen for another two hours to ensure proper reduction. The reactor was heated to about 247 oC at the mid section of the r and hydrogen and DHAA flow started. Table 21 below describes some temperatures, pressure and flow rates for the reaction. Total product collected was 182 g.

Samples were collected and analyzed by GCMS. Reaction parameters and products seen in GCMS are shown in Tables 21 and 22 respectively. Table 23 below describes compounds seen in the GCMS qualitative analysis and gives an estimation of the calorific value of a product sample of the reaction. 100% of DHAA was hydrogenated. 73% of product was ed to contain higher ls, alkanes and ketone products, 14% was higher alcohols.

Experimental calorific values of samples run gave S4 34.2MJ/Kg, S8 34.5 MJ/Kg, S11 34.5MJ/Kg.

Time Reactor He DHAA H2 DHAA Temp. Temp. Temp pressure re Flow flow Temp. Top Mid bottom psi psi rate rate oC oC oC oC 1:51 305 311 3.1 12.2 138 200 247 219 2:03 304 311 3.6 18.2 142 195 236 220 2:14 303.6 308 3.0 20 142 201 262 314 2:24 301 306 3.0 20.8 141 213 243 373 2:37 302 307 3.0 16.8 137 234 299 345 2:48 299 292 3.0 17.4 138 261 385 356 2:58 300 306 3.1 17.2 141.9 241 332 351 3:09 297 303 3.1 16.4 140.9 259 369 353 Hydrogen cylinder replaced. 3:22 303.9 309 3.4 16.1 143 306 356 281 3:35 305 310 3.3 16.5 144 147 202 265 3:47 92 309 -7 16.9 146 221 267 368 Table 21. Reaction parameters for Cu-Zn run 4 hydrogenation of DHAA Ret GCMS nd Time,min Area % Heptane 6.51 3.87% nol 6.92 4.72% 2-Pentanone 7.18 6.48% 2-Pentanol 7.51 7.25% 4-Heptanone 10.89 16.14% 2-Heptanone 11.28 18.29% 4-Propylheptane 11.47 10.82% 4-Nonanone 14.47 3.40% 4-Nonanol 14.72 2.10% 73.1% of sample is shown here Energy G /K 1 5 5 7 0 0 2 J .8 M 0.00 0.00 0.00 1. 6 4. 9 0. 9 11.58 2.35 10.00 9. 0 1. 3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 4 1 L weighted Net A T G 0 0 4 7 0 0 2 T O Net Energy /K J . 0 . 3 . 1 . 1 . 5 .8 M 0.00 0.00 0.00 36 3 4 36 41.89 38.74 46.44 5 4 1 4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 4 1 wt y % % 2 % 9 % % % % % b 0.00% 0.00% 0.00% 6 3 3 0 .0 4 . 4 . 4 . 0 0 1 4 2 . 6 27.65% 6.08% 21.54% 2 0 3 . 1 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 .0 1 0 weighted Net G /K MJ 0 6 rg y 0.00 0.00 0.00 0.00 0.00 0.00 0.16 0.58 0.32 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 .0 0 .0 1 n e E ls n o Ph e Net Energy G 4 J /K .8 M 33.18 34.39 36.66 34 t y w % % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.49% 1.69% 0.86% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 4 .0 3 weighted Net Energy G /K 0 1 J .7 M 0.00 0.00 0.00 0.00 2.53 0.14 0.78 0.27 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 3 C G 4 MI S Net Energy /K J .0 M 32.82 27.94 47.53 35.24 35 wt % 0 % % b y 0.00% 0.00% 0.00% 0.00% 7.71% 0.50% 1.64% 0.75% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 .0 0 .6 10 weighted Net Energy G /K 0 9 J .0 .8 M 0.00 0.00 0.00 0.00 2.42 0.50 6.42 0.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 9 e s G 7 to n /K J .1 K e Net Energy M 0.00 36.00 37.45 39.00 39.40 38 w t % % 1 % b y 0.00% 0.00% 0.00% 0.00% 6.71% 1.33% 16.45% 1.42% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 25 .9 weighted Net Energy /K G 0 9 .2 M J 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.14 1.73 3.98 1.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 7 s t ic G 0 m a J /K 0.00 42.10 42.60 42.90 42.30 41.50 0.00 .3 42 A r o Net Energy M y wt % 3 % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.33% 0.34% 4.02% 9.40% 3.13% .0 0 0 17 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% .2 weighted Net Energy 3.37 G 0 0 J /K 0.28 7.96 5.10 .0 .7 M 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 16 s n e G 4 lk a /K J A Net Energy 0.00 48.17 47.60 47.80 47.70 0.00 0.00 0.00 0.00 47 0.00% 0.00% 0.00% 6.99% 0.59% 16.65% 10.69% t w y % % 1 % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 .9 34 1.61 0.00 0.31 0.72 0.53 0.00 0.00 G /K 0 7 .1 M Energy J 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 weighted Net 3 36.00 0.00 39.10 41.08 40.70 0.00 Net Energy G ls /K o h 0 o .1 M J A lc 38 4.46% 0.00% 0.80% 1.75% 1.30% 0.00% 0.00% wt y % % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 .0 1 0 8 .3 4 5 6 7 8 9 10 's L of C 1 2 3 11 12 13 14 15 16 17 18 19 0 2 T A # T O Table 22. Products in GCMS samples of DHAA Cu-Zn ion experiment run 4 sample #8.

Experiment 21: Hydrogenation of DHAA over a copper zinc catalyst at lower DHAA flow rates: The reactor was filled with 580 g of copper zinc catalyst and reduced with 5% hydrogen 95% nitrogen overnight at 195 oC. The reduction was continued by replacing the hydrogen/argon mixture with hydrogen for another two hours to ensure proper reduction. The reactor was heated to about 300 oC at the mid section of the reactor and hydrogen and DHAA flow started. Table 24 below describes some temperatures, pressure and flow rates for the reaction. 301 g of DHAA was d. Sixteen liquid samples were collected over the reaction amounting to 117 g of t collected. Samples were collected and analyzed by GCMS.

Reaction parameters and products seen in GCMS are shown in Tables 24 and 25 respectively and Figure 19 below. Table 26 below describes compounds seen in the GCMS qualitative analysis and gives an estimation of the calorific value of a product sample of the reaction. 100% of DHAA was converted. 75% of product ed hydrocarbons and 2% of nol. Figure 19 shows composition change of the mixture of the formed products with time and temperature.

Time Reactor He DHAA H2 flow DHAA Temp. Temp. Temp pressure re Flow rate rate Temp. oC Top oC Mid oC bottom psi psi oC 1:40 300 308 2.3 21.3 151 216 298 309 1:50 304 311 1.8 19.8 150 218 354 383 2:00 306 311 1.9 20.8 150 219 360 361 2:10 306 311 1.2 21.6 148 216 336 379 2:20 308 314 2.0 22.1 147 220 276 327 2:30 306 311 1.6 20.2 147 233 329 311 2:40 302 306 2.1 19.3 146 224 416 309 2:50 303 308 1.9 20.0 144 219 434 304 3;00 299 306 2.2 27.6 145 189 400 315 3:10 302 308 2.1 27.9 145 139 283 342 3:20 300 308 2.6 23.1 144 167 311 349 3:30 298 303 1.9 22.4 144 210 294 301 3:40 299 303 1.8 19.8 145 249 334 267 3:50 299 301 1.4 20.6 145 254 347 287 4:00 299 304 1.2 20.6 145 218 311 295 Table 24. Reaction conditions for DHAA Cu-ZnO hydrogenation run 11 as flow of DHAA was varied.

Energy G /K . 4 5 9 2 9 4 0 . 5 6 M J 0.00 0.00 0.00 0.07 0.66 0.21 19 8.72 8.71 5. 7 0. 9 1. 4 0.00 0. 5 0.00 0.00 0.00 0.00 0. 0 6 4 0.00 L weighted Net T A G 1 2 3 7 0 0 6 T O Net Energy /K . 8 . 9 . 5 . 6 . 5 . 5 M J 0.00 0.00 0.00 28.84 38.64 34.54 4 7 46.99 45.61 5 4 4 2 4 6 0.00 7 4 0.00 0.00 0.00 0.00 0. 0 6 4 0.00 wt y 0.00% 0.00% 0.00% 0.25% 1.71% 0.62% 8 % % % % % % % . 6 0 7 9 3 0 . 0 0 2 . 6 . 1 2 . 1 3 0.00% 1 . 1 0.00% 0.00% 0.00% 0.00% 0. 0 0 0 0.00% ed Net % b 4 18.57% 19.09% 1 1 Energy /K G 0 7 M J 0.00 0.00 0.00 0.07 0.57 0.09 0.00 0.47 0.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 1. 6 0.00 C G 1 MI S Net Energy /K J . 8 M 28.84 38.78 27.94 38.32 45.30 38 wt y % % % b 0.00% 0.00% 0.00% 0.25% 1.47% 0.33% 0.00% 1.23% 1.03% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 0 4. 3 0.00% weighted Net Energy /K G 0 7 M J 0.00 0.00 0.00 0.00 0.00 0.00 0.46 0.00 0.61 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 1. 0 s e n G 8 t o /K . 6 e J K Net Energy M 0.00 0.00 0.00 39.00 0.00 40.20 39 wt y % % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 1.17% 0.00% 1.53% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 2. 7 0 weighted Net Energy /K G 0 8 J M 0.00 0.00 0.00 0.00 0.00 0.12 0.28 0.00 1.09 1.75 0.75 0.18 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 4. 1 ic s a t G 5 m /K . 2 r o J 41.90 42.10 0.00 42.90 42.30 41.50 41.50 42 A Net Energy M w t % % % b y 0.00% 0.00% 0.00% 0.00% 0.00% 0.29% 0.65% 0.00% 2.55% 4.14% 1.80% 0.44% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0. 0 0 9. 8 9 weighted Net Energy /K G 9 . 5 0 M J 0.00 0.00 0.00 0.00 0.00 0.00 18.71 8.25 5.58 4.03 0.17 1.31 0.00 0.54 0.00 0.00 0.00 0.00 0.00 0. 0 38 0.00 s e n G 1 lk a J /K . 9 A Net Energy M 48.17 47.60 47.80 47.70 47.60 47.50 0.00 47.50 47 w t y % 5 % % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 17.34% 11.66% 8.46% 38.85% 0.37% 2.75% 0.00% 1.13% 0.00% 0.00% 0.00% 0.00% 0.00% 0 0. 0 . 5 80 0.00 0.00 0.00 0.00 0.09 0.00 weighted Net Energy G /K 0 5 M J 0.00 0.00 0.96 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0 1. 0 0.00 37.80 0.00 o ls h G 7 o lc J /K . 9 A Net Energy M 0.00 0.00 41.30 40 0.00% 0.00% 0.00% 0.00% 0.24% 0.00% t w y % % % b 0.00% 0.00% 2.32% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% . 0 0 6 0 2. 5 1 2 3 4 5 6 's f C L o 7 8 9 10 11 12 13 14 15 16 17 18 19 0 2 A T Table 26. GCMS data of DHAA Cu-Zn hydrogenation run 11 sample 1 products with estimation of calorific value of th emixture # T O Compound Ret GCMS Time,min area % Heptane 6.51 37.80% 2-Methylheptane 7.87 2.51% 3-Methylheptane 8.04 6.87% Ethylcyclohexane 9.48 2.90% 3-Ethylheptane 10.03 3.25% Nonane 10.57 7.51% 4-Propylheptane 11.46 3.12% 4-Methylnonane 11.77 3.47% 6-Methyltridecane 13.34 2.82% Undecane 14.17 2.60% 4-Nonanol 14.74 2.30% Table 25. Products seen in GCMS samples of DHAA ion run 11 sample #1 Butyric Acid zation and Hydrogenation: Experiment 22: Ketonization of c acid over gamma-alumina in a continuous flow reactor: Ketonization and Hydrogenation Reactor system setup: The ketonization reaction was performed in a steel tube reactor (made from ok parts) consisting of a ½” diameter stainless steel tube fitted with a ball valve at the bottom and a 1/4” union stainless steel cross on the top. A thermocouple was attached to the top arm of the cross with one of the (cross) side arms bearing a pressure gauge, pressure relief valve and a ball valve. The other side arm of the ¼” union cross was connected to a 1/16” tube which was attached to a Gilson 307 HPLC pump.

The 1/16” tube entered the reactor and extended down till it was just above the catalyst bed. The bottom arm of the cross was ed to the top of the ½” stainless steel tube. The tube was wrapped with heating rope and insulation was wrapped around the heating rope. Another thermocouple was placed under the heating rope. Both the thermocouples were connected to a digital display. The ball valve on the bottom of the reactor is connected to a coil of 1/8” ess steel tube that was connected to 2” length of ¼ inch tube with a drain at its bottom for liquid condensate and a vent near its top that carried out non-condensing gases. This coiled tube and lower portion are cooled with ice water and served as a trap to collect liquid. The end of the gas vent had a ball valve and the liquid collecting end had a needle valve so that it could be opened slowly to collect liquid samples. 4.1 g of gamma-alumina was loaded into the reactor and three different runs were done for the ketonization.

Run a) The reactor was heated to 350 oC. The HPLC pump was turned on and butyric acid was pumped at a rate of 0.25 ml/min. After the reaction had run for 15 minutes liquid samples were drawn. GCMS of the s indicated formation of 6.5% 4-heptanone with 80% butyric acid remaining indicating a conversion of about 7.5% by GCMS.

Run b) The experiment was run with the flow rate of butyric acid decreased to 0.1ml/min from 0.25 ml/min with temperature raised to 420 to 460 oC. GCMS samples indicated 49% heptanone and 40% butyric acid indicating a conversion of about 55%.

Run c) The experiment was run with a flow rate of 0.05ml/min, the temperatures ranged from 410 to 460 oC. Samples of the reaction were collected. GCMS analysis of the product indicated 72.5% 4-heptanone was formed and 5.4% butyric remained indicating a conversion of about 93%.

Results are summarized in the Table 26 below: Butyric acid Reaction 4-Heptanone Butyric acid Exp.

Temp. oC flow rate Conversion Area % Area % No. ml/min Run a 350 0.25 6.5 80 7.5 Run b 0 0.10 49 40 55 Run c 410-460 0.05 72.5 5.4 93 Table 27: Heptanone t vs butyric acid starting material GCMS analysis as flow rate is varied.

Reduction of 4-heptanone to 4-heptanol: ] ment 23: ion of 4-Heptanone to 4-heptanol over a copper-zinc catalyst in a continuous flow reactor: The reduction reaction was performed in a hydrogenation reactor (Fig. 14) (made from Swagelok parts using the required unions, port connectors, reducers and valves as needed) consisting of a ½” diameter ess steel tube reactor d in heat tape and tion fitted with a ball valve at the bottom and a cross on the top. A thermocouple 6 was attached to the top arm of the cross. One of the side arms was connected to a pressure gauge , pressure relief valve and a ball valve to feed en to the reactor. To control the flow rate of hydrogen, the ball valve was connected via 5 foot length of fine 0.005” id tubing 3 connected by additional flexible tubing to a pressure gauge and a en cylinder. A 1/16” tube for liquid feed to a Gilson 307 HPLC pump was fed from a reactant reservoir. The 1/16” tube entered the reactor and extended down until it was just above the catalyst bed. The bottom arm of the cross union was attached to the top of the ½” stainless steel reactor tube. The tube was wrapped with heating rope and insulation was d around the g rope. Another thermocouple was placed under the heating rope. Both the couples were connected to a digital display. The ball valve on the bottom of the r is connected to a coil of 1/8” stainless steel tube 7 that was connected to short length of ¼ inch tube with a drain at its bottom for liquid condensate and a vent near its top that carried out non-condensing gases. This coiled tube and lower portion are cooled with ice water and served as a trap to collect liquid. The end of the gas vent coming out of the top of the trap had a back pressure valve to control reactor pressure and maintain the required flow rate of hydrogen h the reactor which was calibrated for flow rates at different pressures before the reaction. The liquid collecting vent tube coming out of the bottom of the trap had a needle valve so that it could be opened slowly to collect liquid samples.

Procedure: The reactor tube was filled with about 13 g of zinc copper oxide st (Unicat MTS401) and the catalyst reduced in 95:5 N2/hydrogen stream at 0.2 liters/min ght at a temperature of 180 oC. The N 2/hydrogen mixture was replaced by a hydrogen line and reduction continued for another hour and then d. The reactor pressure was set to 300 psi en with temperature at 175 oC. en flow was at 400 cc/min and the HPLC pump was started, pumping 4-heptanone at a rate of 0.2 ml/min. Reaction was continued for about 90 minutes at this flow rate as samples were taken and analyzed by GCMS indicating 83.7 % heptanol and 9.2% heptanone remaining (~90% conversion by GCMS). Flow rate of 4-heptanone was lowered to 0.15ml/min as temperature, reactor pressure and en flow rate were in the range of 180-190 oC, 300 psi and 400cc/min respectively. GCMS at the lower flow rate indicated 77.8% 4-heptanol and 5.3% heptanone which is about 93% conversion by GC. A total of 22 grams of 4-heptanone were pumped through the reactor and 20 g of liquid product mixture was collected.

Experiment 24: Synthesis of Hydrocarbons from butyric acid on larger scalereactor setup: A reaction system (shown in Fig. 18) consisting of two steel pipes, reactor 1 (R1) and reactor 2 (R2) connected in series was built to prepare heptane, 4-heptanol, and 4-heptanone.

The first reactor R1, contained catalyst to ketonize butyric acid and pass the resulting product containing heptanone to the second reactor R2 containing catalyst which reduced 4-heptanone to form 4-heptanol, heptane, etc. R1 was made of a 1” diameter ASA schedule 40 pipe, 12 inches in length having connections for thermocouples (6,7,8,9) on its side that measured catalyst bed temperatures along with a pressure transducer (5). The top of the tube was connected to a 1/8th inch tube which fed c acid onto the catalyst bed. The 1/8th” tube was connected via a 1/16th inch tube (3) to a steel bottle containing butyric acid under a pressure using differential pressure transducer (4) used to r butyric acid a different rates. The bottom of the tube R1 was connected via a 1/4” inch tube to R2 which was ASA le 40 about 13 inches in length and diameter of 1.5 inches having connections for thermocouples (14, 15, 16, 17, 18, 19) on its side that measured catalyst bed temperatures along with a pressure transducer (13). A hydrogen line with a 0.09”orfice (10) connected to flow controller (11) entered R2 at the top. The bottom of R2 was connected to a trap that condensed the liquid products of the reactors and conveyed the gaseous products out to a vent. The trap was cooled by circulating chilled liquid and contained an outlet at the bottom that was connected to a ball valve and needle valve in series so that liquid samples could be drawn off slowly. The gas outlet from the trap was connected to a back pressure valve (21) so that r pressure could be set at 300 psi or other pressures as desired.

A gas flow meter (22) was added down stream from back pressure control valve (21). Reactor R1 was filled with 80 g of gamma-alumina and R2 was filled with 570 g of copper zinc oxide catalyst (MTS-401 Unicat). The catalyst bed in R2 was heated to 180 oC and a stream of 5% hydrogen in nitrogen was passed over the st for about 16 hours to reduce it. Pure hydrogen was passed for an additional hour to complete reduction.

Reactions were run as butyric acid was fed into R1 at 1 ml/min and after ketonization ed the output of R1 was fed along with hydrogen flow rates at 4 SLPM through R2. Reactor re was at around 300 psi and ature was raised. Samples of the reaction were drawn and analyzed by GCMS.

Five experiments were run with typically more than 25 samples for each run.

Thus more than 125 samples were taken. For instance, data from run 3 was charted in Figure 20 below g product composition of s as the temperature changed and experiment progressed over time. Table 28 shows an example of deeper analysis of data points from Figure for sample 30 taken at around 15:14 on the x-axis. GCMS qualitative analysis shows the important compounds found in sample 30 listed along with their percentage. 100% of starting als were converted. Product mixture shows above 95% arbons of which 72.5% is heptane and minor ketone products. Table 29 lists experimental calorific values of samples from ent runs.

Table 30 shows a theoretical energy calculation for the same sample 30 based on GCMS qualitative analysis. The table shows distribution of classes of compounds in the sample such as ls (such as 1-butanol, 4-heptanol, etc), ketones (such as 4-heptanone), alkanes (such as heptane, nonane, etc).

GC Ret.

Time Compound Area % 6.50 Heptane 72.5% 7.90 4-Methylheptane 1.3% 8.03 3-Methylheptane, 4.8% 8.56 Octene 0.54% 9.41 Acetylacetone 0.54% .03 3-Ethylheptane 1.1% .56 Nonane 1.8% 11.46 4-Propylheptane 4.0% 13.13 2,4-Heptanedione 0.54% 13.33 Tridecane, 6-methyl- 9.9% Table 28. GCMS data of products in run 3 sample 30 of butyric acid Ketonization-hydrogenation reaction.

Expt. Avg. of Sample Alcohols Alkanes Ketones Aromatics Estimated Experimental Run No. Top Three weight Area % Area % Area % Area % fic Calorific Value and Temps. gms. Value KJ/Kg KJ/Kg Sample oC BR01 222 4.1gm 28.54 4.55 24.4 - 32,330 26,484 BR 01 281 8.8gm 45.87 24.23 15.8 1.14 37,570 35,766 BR 02 305 4.1gm 40.22 31.44 18.4 - 38,400 36,196 BR 02 317 1.3gm 14.82 63.48 12.4 4.01 41,590 40.524 BR 03 251 9.4gm 57.00 7.56 17.2 8.18 36,710 35,494 BR 04 184 8.3gm 28.97 4.55 26.34 33.88 37,870 30,580 BR 04 244 20.9gm 54.59 3.99 30.4 - 36,420 34,052 BR 05 155 3.50gm 7.79 8.73 68.9 - 36,850 37,100 BR 05 254 9.40gm 24.49 6.41 56.8 0.67 35,930 30,108 BR 05 308 10.1gm 18.33 22.43 51.7 - 37,650 35,977 Table 29: Butyric acid ketonization-hydrogenation reaction experimental calorific values of samples, composition and calculated values 9 4 G 2 . 0 0 5 7. 4 2 9 6 3 6 8 4 42 .0 weighted Energy /K J . 3 . 6 . 1 . 5 . 9 .4 . 2 .1 K 0 1 0 26 1 1 2 0 L T A . 1 1 5 3 G 0 0 0 5 0 2 8 0 6 . 0 .3 /K 5 . 0 . 4 0 . 0 6 . 6 . 7 7 .3 1 . 1 4 .6 7 T O 4 46 40 Net Energy J K 3 3 3 43 2 4 4 4 % % % wt % . 2 % % % % % % 0 y % % % % % % % % % % % % 0 6 . 2 . 8 1 0. 0 0. 0 0. 0 0 .0 0. 0 0. 0 10 % b 0 . 9 0. 0 0 .0 0. 0 . 6 5 . 5 0 0. 0 0 6 7 . 0 .5 3 . 2 5 .3 0 0. 0 G 1 7 .3 weighted Net Energy /K . 3 7 K J 1 c id 0 G 0 A 24 .8 Net Energy /K . 8 K J 4 2 0 % % % % % % % wt % % % % % % % % % % % % 0. 0 0 0. 0 0. 0 0 0 0. 0 0 0. 0 0 .0 0 0. 0 0 0 0. 0 1 .5 5 y % b . 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0. 0 .0 0 0. 0 . 5 5 0. 0 0. 0 0. 0 . 0 0 .0 0 0. 0 0 .0 0. 0 G 0 .1 7 7 J /K K 0. 1 ls weighted Net Energy o e n 0 .5 G /K 0 . 5 P h 35 Net Energy J K 35 % 0 % 0 % 0 0 % 0 % 0 % % 0 % 0 % 8 y wt 0 % 0 % 0 % % 0 % 0 0 % % 0 % 8 % 0 0 % 0 % % 0 0 . 0 . 0 0 0. 0 0. 0 0. 0 0 .0 0. 0 0. 0 .4 0 % b 0. 0 .0 0 0. 0 0. 0 0. 0 0. 0 0 . 0 0. 4 0 .0 . 0 0 0 .0 0. 0 0 G 1 0. 0 9 5 7. 4 1 4 7 4 43 .6 weighted Net Energy /K J . 0 .5 .1 K 29 3. 0 1 2. 3 0 e s n 1 5 1 G 0 0 0 0 lk a . 1 . 0 . 2 /K . 2 . 6 ..8 . 7 . 6 A 46 46 47 Net Energy J K 48 47 47 47 47 % 0 % 7 % % % % 6 % wt % % % % % 8 % % % % % % . 2 . 1 0 0 0 .3 0 y 0 0 0 0 0 . 1 2 3 6 9 0 1 6 0. 0 0. 0 0. 0 0. 0 0. 0 91 0 0. 0 % b 0. 0 0. 0 0. 0 0 . 0 0. 0 0. 0 0 6 . 3 6 3. 2 . 9 4 0 . 2 0. 0 .1 G 0 5 /K 2 .1 2 K J 0. 0 0 ls weighted Net Energy h o o G 0 2 6 lc /K . 0 . 3 . 6 A Net Energy J K 36 41 38 0 % % % % % wt % % % % % % % % % % % . 0 . 0 0 0 0. 0 0 0 . 3 y 0 0 6 0 0 0 0 0 0 0 0 0 6 0 0. 0 0 0 % b 0. 0 0. 0 0. 0 . 0 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 .3 0 weighted Net Energy /K G 6 2 9 J 0. 1 .3 0. 2 0 e s n G 0 0 5 e t o /K . 0 . 1 .5 K Net Energy J K 36 39 37 w t y % % % % % % % % % % % % % % % % % % Table 30. nd distribution and energy estimation of product for ketonization-reduction run 3 mixture sample 30. % b . 0 0 0 0 5 0 7 0 0 0 0 0 0 0 0 0 0 0 2 0 0 .0 0 . 0 0 . 0 0. 4 . 0 0 0. 5 0 . 0 .0 0 . 0 0 0 .0 0 . 0 . 0 0 0 . 0 . 0 0 0 . 0 . 0 0 .0 0 0 . 0 0 . 0 .0 1 's L o f C ? 1 2 3 4 5 6 7 8 9 0 1 1 1 1 2 1 3 1 4 1 5 6 1 1 7 8 1 1 9 2 0 A T # O T ment 25: Lab scale synthesis of Methyl Ketene: The reactor system (Fig. 16 in drawings) was installed inside of a good working fume hood. The feed stream of propanoic anhydride vapor was generated by addition of the anhydride from the dropping funnel 1 into the hot round bottom flask 2 immersed in an oil bath 3. The ing vapor was passed to the top of a vertical hollow quartz tube 4 47 cm long and with an internal diameter of 22 mm. At the lower part of the quartz tube (5 cm from the bottom) was placed a removable silica foam monolith disk 6 with porosity 45 pores per inch, 20 mm diameter and 10mm thickness. The disk was supported inside of the reactor by a built-in quartz frit and temperature of the disk was measured with an external thermocouple placed in a glass pocket located under the frit. The quartz tube was placed in a cylindrical e 5 where the temperature was controlled with a PID controller 7. The gaseous products produced from the quartz tube were passed through a reflux condenser 8 with cold water (5 oC) to separate the formed methylketene from propanoic acid and anhydride which were ted by a ted cylinder 9 attached at the bottom receiver for liquid condensate.

The top of the reflux condenser was ted to the Dewar condenser 10 equipped with a round bottom flask 11, immersed in a Dewar flask 12. The flask was connected to the second Dewar condenser 13 also equipped with a round bottom flask 14 and immersed in a Dewar flask 15. The flask 14 was connect to the empty bubbler 16 which was attached to a vacuum pump 17 with the outlet tube placed into the hood’s exhausting vent. The furnace ature was set to 650 oC and temperature of the silica foam disk 6 in the reactor was kept at 550– 580 oC. The dropping funnel was charged with 100 mL of propionic anhydride and the vacuum pump was turned on to maintain ~ 80 mbar pressure in the reactor system. The first Dewar condenser 10 and Dewar flask 12 were filled with liquid nitrogen and then the anhydride was added at rate of ~0.8 ml/min to the flask 2 ed in an oil bath heated at 180 – 200 oC. The process was continued for 2h and the product was collected in the flask 11. After the process was stopped, the connection between the first Dewar condenser 10 and a reflux condenser 8 was blocked (by pinching a connecting tubing) and the second Dewar condenser 13 and Dewar flask 15 were filled up with liquid nitrogen. Dewar flask 12 was removed and the round bottom flask 11 with attached Dewar condenser 10 was slowly warmed up to room temperature to distill part of the ted methylketene into the second Dewar condenser 13 and round bottom flask 14. After 1 h the connection between flask 11 and Dewar condenser 13 was blocked and the flask was disconnected and protected with a balloon filled with nitrogen and left overnight. The bubbler 16 was filled with 50 ml of acetone including a few drops of triethylamine. The second Dewar flask was removed and the round bottom flask 14 with attached Dewar condenser 13 was slowly warmed up to room temperature. After 1 h the flask 14 was disconnected, protected with a n filled with nitrogen and left overnight. In the flask 11 was ed 10 g of the yellow liquid ing: 10.4% of methylketene dimer, 51.4% of methylketene , 5.0% propionic acid and 7.4% of propionic acid anhydride (Mixture A). In the flask 14 was obtained 4 g of the yellow liquid including 8.6% of methylketene dimer, 69.5% of methylketene trimer and 7.9% of propionic acid anhydride (Mixture B). The acetone solution in the r 16 showed the presence of triethylamine and only traces of methylketene dimer and propionic anhydride.

Experiment 26: enation of methylketene dimer and trimer over a copperzinc catalyst: The reduction reaction was performed in a hydrogenation reactor (Fig. 14) (made from Swagelok parts using the required unions, port connectors, reducers and valves as needed) consisting of a ½” diameter stainless steel tube reactor wrapped in heat tape and insulation fitted with a ball valve at the bottom and a cross on the top. A thermocouple 6 was attached to the top arm of the cross. One of the side arms was connected to a pressure gauge 5, pressure relief valve and a ball valve to feed hydrogen to the reactor. To control the flow rate of hydrogen, the ball valve was connected via 5 foot length of fine 0.005” id tubing 3 connected by additional flexible tubing to a pressure gauge and a hydrogen cylinder. A 1/16” tube for liquid feed to a Gilson 307 HPLC pump was fed from a reactant reservoir. The 1/16” tube entered the reactor and extended down till it was just above the st bed. The bottom arm of the cross union was attached to the top of the ½” ess steel r tube. The tube was wrapped with heating rope and insulation was d around the heating rope. Another thermocouple was placed under the heating rope. Both the thermocouples were connected to a digital display. The ball valve on the bottom of the reactor is connected to a coil of 1/8” stainless steel tube 7 that was connected to short length of ¼ inch tube with a drain at its bottom for liquid condensate and a vent near its top that carried out non-condensing gases. This coiled tube and lower portion are cooled with ice water and served as a trap to collect liquid. The end of the gas vent coming out of the top of the trap had a back pressure valve to control reactor pressure and maintain the required flow rate of hydrogen through the reactor which was ated for flow rates at different pressures before the reaction. The liquid collecting vent tube coming out of the bottom of the trap had a needle valve so that it could be opened slowly to collect liquid samples.

Procedure: The reactor tube was filled with 8.9 g of copper zinc oxide st (Unicat ) and the catalyst was reduced in 95:5 N2/hydrogen stream at 0.2 liters/min at a temperature of 160 oC for 18 h. The N 2/hydrogen mixture was replaced by a hydrogen line and reduction was continued for another hour at 0.4 liters/min at 200 oC. Then the reactor re was set to 300 psi hydrogen with temperature at 183 oC and hydrogen flow at 400 cc/min. The HPLC pump was turned on and the Mixture A (from the methyl ketene reaction above) was pumped into the reactor at rate of 0.05 ml/min. After 30 min hydrogen flow rate was increased to 660 cc/min and temperature of the reactor to 211 oC and the liquid samples were collected.

GCMS analysis for product taken over duration of on ted formation of 2- methylpentanol, 3-pentanol, pentanone, as two major products of the hydrogenation along with 3-pentanone (6%) and other higher ls ted in smaller amounts. GCMS qualitative analysis of higher alcohols formed is shown in Table 31. 100% of the methyl ketene dimer/trimer mixture was reduced. 43-50% higher l product was formed of which 16-27% was 3- pentanola and 19-28% was 2-methyl pentanol.

GCMS ret. GCMS Area % Compound Time (min) S1 S3 S5 S8 3-Pentanone 7.3 5.7 5.8 6.1 6.4 3-Pentanol 7.4 27.0 18.3 16.5 15.6 2-Methylpentanol 8.9 6.5 4.8 4.4 3.9 Propyl propionate 9.3 4.1 5.8 6.9 6.5 2-Methylpentanol 10.2 12.2 23.1 22.6 19.7 4-Methylheptanone 11.9 2.0 2.3 2.6 2.7 4-Methylheptanol 12.6 2.3 2.2 2.3 2.0 4-Methylheptanol 12.63 1.5 1.9 1.8 1.7 2-Methylpentyl propanoate 13.9 1.9 2.2 2.8 3.1 3,5-Dimethyl furanone deriv. 14.0 1.4 2.1 2.1 2.0 3,5-Dimethyl dihydrofuranone deriv. 14.2 1.4 1.5 1.4 1.4 3,5-Dimethyl dihydrofuranone deriv. 14.3 2.2 1.9 2.7 Propyl 3-hydroxymethyl pentanoate 16.4 1.3 0.9 1.3 1.6 Propyl 3-hydroxymethyl pentanoate 16.6 1.3 1.0 1.3 1.6 Table 31. GCMS product analysis of samples from hydrogenation of methyl ketene dimer.

Experiment 27: Conversion of propanoic acid to 3-pentanol via ketonization and reduction: The continuous flow reactor system (Fig 18) was installed inside of a good working walk-in-hood. In the liquid reservoir was placed 292 g (300 ml) of propanoic acid. In the reactor 1 ization step) was placed 220 g of gamma-alumina (bed of diameter 1.6”and length 13.0”) and in the reactor 2 (reduction step) was placed 570 g copper-zinc oxide catalyst (bed of diameter 1.6”and length 12.4”). Temperature of the reactors 1 and 2 was set at 400 oC and 200 oC, respectively, g begun and the reactor system was pressurized with hydrogen at 300 psi.

The reaction was started and flow of propanoic acid was at about 1.0 ml/min. en flow was at 4.8 SLPM and reactor pressure at 300 psia hydrogen. The ketonization reactor 1 maximum temperature was at 402 oC and average over its entire length was about 360 oC. The hydrogenation reactor 2 maximum temperature was 233 oC and average temperature was 220 oC over its entire .

Product of the reaction was analyzed on a GCMS indicating a mixture with 65% 3-pentanol ing other C4-8 alcohols with about 72% alcohols. Other products were 13% C7-14 aromatics and about 4% pentanone. GCMS ative analysis of products formed is shown in Table 32 and also presents a theoretical estimation of the calorific value of a mixture. weighted Energy /K G 9 8 1 . 5 3 . 9 . 1 . 7 5 4 . 6 .0 M J 0 0 5 2 2.22 0 0 3 6 0.48 1.26 0.30 0.44 2.38 0.86 A L G 0 2 7 5 9 3 O T /K . 0 5 . 4 2 4 . 9 4 . 1 2 . 5 .4 9 T Net Energy M J 3 3 3 36.31 4 3 3 41.48 41.93 42.25 44.52 41.05 42.10 wt % % % % % % % % b y . 7 0 1 0.0% 0.0% 0.0% . 9 2 2 . 0 7 6.1% . 7 1 . 0 2 0.0% 0.0% . 0 0 0 1 1.2% 3.0% 0.7% 1.0% 5.8% 2.0% 0.0% 0.0% 0.0% ed Net Energy G /K 6 .7 M J 0.23 5 0.48 1.26 0.30 0.25 2.38 0.86 ic s t m a Net G /K 5 J . 7 1 A r o Energy M 41.90 4 41.48 41.93 42.25 41.54 41.05 42.10 wt y % % 6 % b 0.00% 0.00% 0.00% 0.00% 0.00% 0.55% 0.00% 0.00% 0.00% 0.00% 0 . 0 0 1 .8 3 1.16% 3.00% 0.70% 0.61% 5.79% 2.03% 0.00% 0.00% 0.00% weighted Net Energy /K G 6 J .7 M 0.58 0 0.18 e s a n G /K .8 5 A lk Net Energy M J 48.20 7 4 47.50 wt % % % b y 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 1.20% 0.00% 0.00% 0.00% 0 . 0 0 8 .5 1 0.00% 0.00% 0.00% 0.38% 0.00% 0.00% 0.00% 0.00% 0.00% weighted Net Energy /K G 1 J .6 M 0.93 24.56 1.48 0.20 0.44 7 2 o ls o h G /K A lc Net Energy J M 36.00 37.80 39.10 40.10 40.70 3 8 w t % 1 % % b y 0.00% 0.00% 0.00% 2.58% 64.97% 3.78% 0.50% 1.08% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0 0.00% . 0 0 7 .9 2 weighted Net Energy /K G 2 .5 M J 1.52 1 e s t o n G 0 .0 /K K e 36.00 Net Energy M J 3 6 0.00% 0.00% 0.00% 0.00% % t 0 w % . 0 y 3 0 4 .2 % b 0.00% 0.00% 0.00% 0.00% 4.23% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% Table 32. GCMS data of propanoic acid Ketonization-hydrogenation products with estimation of calorific value of th emixture 16 17 18 19 0 L 's 2 T A 5 6 f C 4 7 8 9 ? 1 2 3 10 11 12 13 14 15 T O Carbonylation of Alcohols to Acids: The reaction system ts of a) a liquid-phase carbonylation reactor, b) a methyl iodide-acetic acid er column, and c) a flasher. The latter two systems are employed to recover catalyst solutions, methyl iodide and methyl acetate and te product acetic acid.

The carbonylation reactor consists of a stirred autoclave within which the reacting liquid contents are ined at constant level of approximately 1800 ml with contents analyzed periodically. Into this reactor are fed ol, sufficient water and recycled catalyst solution from the flasher and recycled methyl acetate and methyl iodide from the acetic acid methyl iodide splitter column. The composition of the reaction medium is maintained such that there is 13-16% methyl iodide, 4-5 wt.% methyl acetate, 19-19.5 wt.% lithium iodide, 4-5 wt.% water, and 310 to 335 ppm rhodium with the balance of the composition acetic acid which is drawn off as it formed. CO gas containing some hydrogen with a partial pressure of about 20 psi is fed continuously to the system as the mixture is agitated for thorough mixing of gases as reactor pressure is kept at 28 atmospheres with r temperature at 1 oC. Reaction medium is distilled out and acetic acid separated to yield about 14 gram moles of acetic acid/hr/lit of on medium. See Torrence et al, US pat. 4,994,608.

Direct Conversion of Methanol to Ethanol: The autoclave is charged with 0.52 g of rhodium dicarbonyl acetylacetonate, Rh(CO2)acac, (2 mmol), 0.82 g of ruthenium trichloride hydrate, 0.82 g of 1,3bis (diphenylphosphino)propane (2 mmol), 2.5 mL of methyl iodide (40.1 mmol) and 40 mL of ol. The reactor contents are then heated to 140° C. and the pressure adjusted to 1,000 psig using a H2:CO mixture having a 2:1 mole ratio. The reaction is continued for 2.75 hours at 975 ±25 psig and stopped, during which period 3,350 psig of synthesis gas is consumed. The reactor is then cooled and recovered. Analysis of the red liquid product tes formation and presence of about 27.5% ethanol, 10.1% acetaldehyde, 10.2% ethyl acetate, 11.5% methyl acetate, 2.5% acetic acid, 0.5% dimethyl , 1.7% diethyl ether, 11.9% dimethyl ether 17.5% methanol and 2.9% methyl iodide. See Wegman et al, US pat. 4,727, 200.

Carbonylation of Ethanol: The catalyst, RhCl3.3H2O at conc. of 7.63 x 10-6 mol cm-3, ethanol at conc. of 0.69 x 10-2 mol cm-3 and hydroiodic acid at concentration of 0.11 x 10-2 mol are dissolved in water.

The solution is then charged into the reactor, flushed with carbon monoxide and the contents heated to 200 oC temperature within ten minutes. The r is pressurized with 2-3 atm of carbon monoxide and the reaction was started by switching on the stirrer. re in the reactor was maintained using a constant pressure regulator between the reactor and the gas reservoir.

The progress of the on was followed by observing the pressure drop in the reservoir as a function of time. The liquid samples were taken periodically and also analyzed by GC. After absorption 0.7 moles of CO, an is of a liquid phase showed a complete consumption of ethanol and formation of propionic acid with 99% selectivity at about 0.7 x 10-2 mol /cm-3 concentration. See Dake et al, Journal of Molecular Catalysis, 24 (1984) 99-113.

While a number of ary embodiments, aspects and variations have been ed herein, those of skill in the art will recognize certain modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations. It is intended that the following claims are interpreted to e all such modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations are within their scope. The entire disclosures of all documents cited throughout this application are incorporated herein by nce.

References: 1. Organic Synthesis, Coll. Vol. 3, pp 508 (1955). 2. Organic Synthesis, Vol. 20, pp 26 (1940). c sis, Coll. Vol. 3, pp 508 (1955). 3. Organic Letters, 2004, 6(3), 373-376. 4. Journal of American Chemical Society, 2002,124(7),1174-5.

. Journal of American Chemical Society, 2010,132(33),11412-3. 6. The Chemistry of Ketenes, Allenes and Related Compounds, Part 1, 292 John Wiley and Sons, New York (1980). 7. Japan patent, No 47-25065. 8. Journal of al Society, 1952, pp 2563-2568, The Preparation and Dimerization of Methylketene, Jenkins, A.D. 9. Recent advances in process and catalysis for the production of acetic acid, Appl.Cat.A: General, 221, 253-265, 2001.

In this specification where reference has been made to patent specifications, other external documents, or other sources of information, this is generally for the purpose of ing a context for discussing the features of the invention. Unless specifically stated otherwise, reference to such external nts is not to be construed as an admission that such documents, or such sources of information, in any jurisdiction, are prior art, or form part of the common general knowledge in the art.

In the description in this specification reference may be made to t matter that is not within the scope of the claims of the current application. That subject matter should be readily identifiable by a person skilled in the art and may assist in g into practice the invention as defined in the claims of this application.

Claims (20)

CLAIMS What is claimed is:

1. A method for the preparation of an alkyl compound or a mixture of alkyl compounds, the method comprising: a) ing a ketene of the formula I: wherein: each R1 is independently H or C1-6 alkyl; and each R2 is independently H or C1-6 alkyl; b) ng the ketene in a self-addition reaction to form a diketene of the formula II; c) hydrogenating the diketene of the formula II in the ce of a metal catalyst to form the alkyl compound or the mixtures of alkyl compounds.

2. The method of Claim 1, wherein R1 and R2 are hydrogen.

3. The method of Claim 1 wherein butanol is a t.

4. The method of Claim 1 or 2, n the metal catalyst is a transition metal.

5. The method of Claim 2, further sing: a) converting the diketene of the formula II to dehydroacetic acid; and b) reducing the dehydroacetic acid in the ce of a catalyst to form a composition comprising a compound selected from the group consisting of C7, C8, C9, C10, C11, C12, C13 and C14 alkanes, alcohols and ketones, and mixtures thereof.

6. The method of Claim 5, wherein the composition comprising the compound is selected from the group consisting of 2-heptanol, 4-heptanol, ptane-diol, heptane, 2-methyl heptanes, 3-methyl heptane, ethyl cyclohexane, 3-ethyl heptanes, nonane, nonanol, 4-propyl heptanes, 4-methyl nonane, 6-methyl tridecane, undecane, 4-nonanol and mixtures thereof.

7. The method of Claim 6, wherein the catalyst is a transition metal catalyst.

8. The method of Claim 7, wherein the method may be performed in a single reactor or two or more reactors.

9. The method of Claim 7, n the catalyst is selected from the group consisting of a copper chromite barium catalyst, a copper based catalyst and a zinc based catalyst and mixtures thereof.

10. The method Claim 5, r comprising: a) ating the product selected from the group comprising 2-heptanol, 4-heptanol, 2,4-heptane-diol, 2,6-heptane-diol, heptane-triol and mixtures thereof to provide a mixture of unsaturated hydrocarbons; and b) the unsaturated arbons are hydrogenated to form a mixture of hydrocarbons.

11. The method of Claim 2 wherein: a) the diketene is hydrogenated to form a composition comprising butyric acid; b) the composition comprising butyric acid is ketonized to form a composition comprising 4-heptanone; c) the composition comprising 4-heptanone is hydrogenated in the presence of a st to form a composition comprising 4-heptanol and mixtures thereof; and optionally d) the composition comprising 4-heptanol is dehydrated to form a ition comprising 3-heptene; and optionally e) the composition sing 3-heptene is hydrogenated to form a composition sing heptane.

12. The method of Claim 11, n the heptene is further dimerized with a zeolite catalyst to form a C14 alkyl compound.

13. The method of Claim 11, wherein the composition comprising 3-heptene is further isomerized to a mixture of linear and branched heptenes by the treatment with a zeolite catalyst, and the mixture of heptenes is hydrogenated to provide a mixture of linear and branched

14. The method of any one of Claims 11 to 13, wherein all of the hydrogenation steps are performed in a single reactor or a single catalyst bed or both a single reactor and a single catalyst bed or mixtures of catalyst beds.

15. The method of Claim 11, wherein the butyric acid is prepared by a carbonylation reaction of propanol.

16. Alkane compounds prepared by the method of any one of Claims 1 to 15.

17. A fuel composition comprising the alkane compounds of claim 16.

18. A method as claimed in claim 1, substantially as herein described with reference to any example thereof.

19. Alkane nds as claimed in claim 16, substantially as herein described with reference to any example thereof.

20. A fuel composition as claimed in claim 17, substantially as herein bed with reference to any example thereof.