US 20140O81065A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2014/0081065 A1
Sengupta et al. (43) Pub. Date: Mar. 20, 2014
(54) PROCESS FOR MAKING LINEAR LONG Publication Classification
CHAINALKANES USING RENEWABLE
FEEDSTOCKS (51) Int. Cl.
C07C I/22 (2006.01)
(71) Applicant: E DUPONT DE NEMOURS AND (52) U.S. Cl.
COMPANY, Wilmington, DE (US) CPC ........................................ C07C I/22 (2013.01)
USPC .......................................................... 585/733
(72) Inventors: Sourav Kumar Sengupta, Wilmington,
DE (US); Manish S. Kelkar,
Wilmington, DE (US); Kenneth Chad (57) ABSTRACT
Manning, Wilmington, DE (US);
Kenneth Gene Moloy, Hockessin, DE A hydrodeoxygenation process for producing a linear alkane
(US); Andrea M. Perticone, from a feedstock comprising a saturated or unsaturated Cos
Wilmington, DE (US); Joachim C. oxygenate that comprises an ester group, carboxylic acid
Ritter, Wilmington, DE (US) group, carbonyl group and/or alcohol group is disclosed. The
process comprises contacting the feedstock with a catalyst
(73) Assignee: E DUPONT DE NEMOURS AND comprising (i) about 0.1% to 10% by weight of a metal
COMPANY, Wilmington, DE (US) selected from Group IB or VIII of the Periodic Table, and (ii)
about 0.5% to 15% by weight of tungsten, rhenium, molyb
(21) Appl. No.: 14/031,356 denum, Vanadium, manganese, Zinc, chromium, germanium,
Sep.19, 2013
tin, titanium, gold, and/or Zirconium, at a temperature
(22) Filed: between about 150° C. to 250° C. and a hydrogen gas pressure
Related U.S. Application Data of at least 300 psig. By contacting the feedstock with the
catalyst under these temperature and pressure conditions, the
(60) Provisional application No. 61/703,306, filed on Sep. Co-s oxygenate is hydrodeoxygenated to a linear alkane that
20, 2012. has the same carbon chain length as the Cos oxygenate.
US 2014/0081065 A1 Mar. 20, 2014

PROCESS FOR MAKING LINEAR LONG decarboxylated as well as branched products was also
CHAINALKANES USING RENEWABLE observed using processes disclosed in U.S. Pat. Nos. 8,193,
FEEDSTOCKS 400 and 7,999,142.
0001. This application claims the benefit of U.S. Provi 0008 U.S. Pat. No. 8,142,527 discloses a hydrodeoxygen
ation process to produce diesel fuel from vegetable and ani
sional Application No. 61/703,306, filed Sep. 20, 2012, which mal oils requiring a reaction temperature of at least 300° C. A
is incorporated herein by reference in its entirety. hydrodeoxygenation process disclosed by U.S. Pat. No.
FIELD OF THE INVENTION
8,026,401 required a reaction temperature of at least 400° C.
0009. Thus, there continues to be a need for hydrodeoxy
0002 This invention is in the field of chemical processing. genation processes that can be carried out under conditions of
More specifically, this invention pertains to a process for low temperature and pressure, and which reliably convert the
producing linear long-chain alkanes from feedstocks com fatty acids of oils and fats from renewable resources to long
prising Co. is oxygenates such as fatty acids and triglycer chain, linear alkanes without Substantial carbon loss.
ides.
SUMMARY OF THE INVENTION
BACKGROUND OF THE INVENTION 0010. In one embodiment, the invention concerns a hydro
0003 Long-chain alpha,omega dicarboxylic acids (long deoxygenation process for producing a linear alkane from a
feedstock comprising a saturated or unsaturated Co-s oxy
chain diacids, “LCDA) are used as raw materials in the genate comprising a moiety selected from the group consist
synthesis of a variety of chemical products and polymers ing of an ester group, carboxylic acid group, carbonyl group,
(e.g., long-chain polyamides). The types of chemical pro and alcohol group. This process comprises contacting the
cesses used to make long-chain diacids have a number of feedstock with a catalyst comprising (i) about 0.1% to about
limitations and disadvantages, not the least of which is the 10% by weight of a first metal selected from Group IB or VIII
fact that these processes are based on non-renewable petro of the Periodic Table, and (ii) about 0.5% to about 15% by
chemical feedstocks. Also, the multi-reaction conversion pro weight of a second metal selected from the group consisting
cesses used for preparing long-chain diacids generate of tungsten, rhenium, molybdenum, Vanadium, manganese,
unwanted by-products resulting in yield losses, heavy metal Zinc, chromium, germanium, tin, titanium, gold and Zirco
wastes and nitrogen oxides which need to be destroyed in a nium, at a temperature between about 150° C. to about 250°
reduction furnace.
C. and a hydrogen gas pressure of at least about 300 psig. By
0004 Given the high cost and increased environmental contacting the feedstock with the catalyst under these tem
footprint left by fossil fuels and the limited petroleum perature and pressure conditions, the Co- oxygenate is
reserves in the world, there is heightened interest in using hydrodeoxygenated to a linear alkane that has the same car
renewable sources such as fats and oils obtained from plants, bon chain length as the Cos oxygenate. Optionally, the
animals and microbes to make chemical products and poly hydrodeoxygenation process further comprises the step of
mers such as long-chain diacids. recovering the linear alkane produced in the contacting step.
0005 Long-chain diacids can be made from long-chain 0011. In a second embodiment, the Cos oxygenate is a
alkanes, which in turn can be made by converting fatty acids fatty acid or a triglyceride.
and triglycerides via hydrodeoxygenation (HDO). The 0012. In a third embodiment, the feedstock comprises a
alkane products of this reaction not only can be used to plant oil or a fatty acid distillate thereof. In a fourth embodi
produce long-chain diacids, but are also useful as fuel by itself ment, the feedstock comprises (i) a plant oil selected from the
or in a mixture with diesel from petroleum feedstocks. group consisting of soybean oil, palm oil and palm kernel oil;
0006 Conventional deoxygenation processes for convert or (ii) a palm fatty acid distillate.
ing renewable feedstocks to long-chain alkanes include cata 0013 In a fifth embodiment, the Cos oxygenate is palm
lytic hydrodeoxygenation, catalytic or thermal decarboxyla itic acid, myristic acid, or lauric acid. The linear alkane pro
tion, catalytic decarbonylation and catalytic hydrocracking. duced by the hydrodeoxygenation process in this embodi
Commercially available deoxygenation reactions are typi ment is, respectively, hexadecane, tetradecane, or dodecane.
cally operated under high pressure and temperature in the 0014. In a sixth embodiment, the catalyst comprises about
presence of hydrogen gas, rendering the process to be quite 1% to about 6% by weight of platinum as the first metal and
expensive. A few low pressure deoxygenation processes have 1.5% to about 15% by weight oftungsten as the second metal.
also been described; however, such processes suffer from In a seventh embodiment, the catalyst comprises about 4% to
several disadvantages such as low activity, poor catalyst sta about 6% by weight of platinum as the first metal and about
bility, and undesirable side reactions. Typically, these pro 1.5% to about 2.5% by weight of tungsten as the second
cesses require a high temperature and result in a high degree metal. In an eighth embodiment, the catalyst comprises about
of decarboxylation and decarbonylation, leading to shorten 5% by weight of platinum as the first metal and about 2% by
ing of chain length of the long-chain alkane products. weight of tungsten as the second metal. In a ninth embodi
0007 For example, U.S. Pat. Appl. Publ. No. 2012 ment, the catalyst comprises about 2% by weight of platinum
0029250 discloses a deoxygenation process that produces as the first metal and about 5% to about 10% by weight of
pentadecane (C15:0) and heptadecane (C17:0) from palmitic tungsten as the second metal.
acid (C16:0) and oleic acid (C18:1), respectively, via decar 0015. In a tenth embodiment, the catalyst further com
boxylation. This process also required a reaction temperature prises a Solid Support. In an eleventh embodiment, the Solid
of at least 300° C. Besides resulting in products with carbon Support comprises alumina (Al2O).
loss, the deoxygenation process also resulted in incompletely 0016. In a twelfth embodiment, the temperature of the
deoxygenated products such as Stearic acid, unsaturated iso hydrodeoxygenation process is about 200° C. and the pres
mers of oleic acid, and branched products. The formation of sure is about 400 psig.
US 2014/0081065 A1 Mar. 20, 2014

0017. In a thirteenth embodiment, the feedstock and the comprised in the Co-s oxygenate in the form of one or more
catalyst are contacted in an organic solvent. In a fourteenth alcohol, carbonyl, carboxylic acid, ester, and/or ether moi
embodiment, the organic solvent comprises tetradecane, eties. As would be understood in the art, the carboxylic acid,
hexadecane, or a mixture thereof. ester, and/or ether moieties, if present, would be located at
0018. In a fifteenth embodiment, the molar yield of the one or both termini of the Cos oxygenate.
hydrodeoxygenation process is less than 10% for a reaction 0027. Although the Co-oxygenate can be 10, 11, 12, 13,
product having a carbon chain length that is one or more 14, 15, 16, 17, or 18 carbonatoms in length, it typically has an
carbon atoms shorter than the carbon chain length of the even length of 10, 12, 14, 16, or 18 carbon atoms. Examples
Clos OXygenate. of Cos oxygenates as referred to herein include, but are not
limited to, esters, carboxylic acids, ketones, aldehydes and
DETAILED DESCRIPTION OF THE INVENTION alcohols.
0019. The disclosures of all patent and non-patent litera 0028. A “saturated Co-oxygenate' as used herein refers
ture cited herein are incorporated herein by reference in their to a Cos oxygenate in which the constituent carbon atoms
entirety. are linked to each other by single bonds (i.e., no double or
0020. As used herein, the term “invention' or “disclosed triple bonds). An example of a Saturated Cos oxygenate is
invention' is not meant to be limiting, but applies generally to stearic acid (C18:0).
any of the inventions defined in the claims or described 0029. An "unsaturated Co. oxygenate' as used herein
herein. refers to a Cos oxygenate in which one or more double
0021. The terms “hydrodeoxygenation” (HDO), “hydro (alkene) or triple (alkyne) bonds are present in the carbon
deoxygenation process or reaction”, “deoxygenation process atom chain of the Cos oxygenate. Examples of unsaturated
or reaction' and “hydrotreating are used interchangeably Co- oxygenates are oleic acid (C18:1) and linoleic acid
herein. Hydrodeoxygenation as used herein refers to a chemi (C18:2), which contain one and two double bonds, respec
cal process in which hydrogen is used to reduce the oxygen tively.
content of an oxygen-containing organic compound Such as 0030. An “ester group’ as used herein refers to an organic
an ester, carboxylic acid, ketone, aldehyde, or alcohol. Com moiety having a carbonyl group (C=O) (defined below)
plete hydrodeoxygenation of Such compounds typically adjacent to an ether linkage. The general formula of an ester
yields an alkane, in which the carbon atom(s) that previously group is:
was bonded to an oxygenatom becomes hydrogen-Saturated
(i.e., the carbonatom has become “hydrodeoxygenated). For
example, hydrodeoxygenation of a carboxylic acid group or
an aldehyde group yields a methyl group (-CH), whereas
hydrodeoxygenation of a ketone group yields the internal
carbon moiety —CH2—.
0022. The hydrodeoxygenation process as described The Rin the above esterformula herein refers to a linear chain
herein also reduces alkene (C—C) and alkyne (C=C) groups of 9-17 carbonatoms; in this manner, the C=O carbonatom
to C-C groups. Thus, the hydrodeoxygenation process can represents the tenth to eighteenth carbon atom of a Cos
also be referred to as a process of reducing sites of unsatura oxygenate that contains an ester group. The R' group refers to
tion in organic compounds. an alkyl oraryl group, for example. Examples of ester groups
0023. As used herein, hydrodeoxygenation does not refer are found in mono-, di- and triglycerides which contain one,
to a process that reduces the oxygen content of a hydrocarbon two, or three fatty acids, respectively, esterified to glycerol.
through breaking a carbon-carbon bond. Such as would occur With reference to the above formula, the R' group of a
with the removal of a carboxylic acid group (i.e., decarboxy monoglyceride would refer to the glycerol portion of the
lation) or carbonyl group (i.e., decarbonylation). Neither does molecule. A linear alkane produced from an ester by the
hydrodeoxygenation herein refer to a process that incom disclosed hydrodeoxygenation process contains the carbon
pletely reduces an oxygenated carbon moiety (e.g., reduction atoms of the R group and the C=O group.
of a carboxylic acid group to a carbonyl or alcohol group). 0031. A "carboxylic acid group' or “organic acid group'
0024. The terms “alkane”, “paraffin', and “saturated as used herein refers to an organic moiety having a "carboxyl
hydrocarbon are used interchangeably herein. An alkane as or “carboxy' group (COOH). The general formula of a car
used herein refers to a chemical compound that consists only boxylic acid group is:
of hydrogen and carbon atoms, where the carbon atoms are
bonded exclusively by single bonds (i.e., they are saturated
compounds). O
0025. The terms “linear alkane”, “straight-chain alkane'. |
C
“n-alkane', and “n-paraffin' are used interchangeably herein R OH
and refer to an alkane that has only two terminal methyl
groups and for which each internal (non-terminal) carbon
atom is bonded to two hydrogens and two carbons. The short The R in the above carboxylic acid formula refers to a linear
hand formula for a linear alkane is C.H. Linear alkanes chain of 9-17 carbon atoms; in this manner, the carboxyl
differ from branched alkanes, which have three or more ter group (COOH) carbonatom represents the tenth to eighteenth
minal methyl groups. carbon atom of a Cos oxygenate that contains a carboxylic
0026. The term "Cos oxygenate' as used herein refers to acid group. A linear alkane produced by the disclosed hydro
a linear chain of 10-18 carbon atoms in which one or more deoxygenation process retains the carboxyl group carbon
carbon atoms is bonded to an oxygen atom (i.e., one or more atom (i.e., the product is not decarboxylated relative to the
oxygenated carbons). Such oxygen-bonded carbonatoms are Co-s oxygenate Substrate).
US 2014/0081065 A1 Mar. 20, 2014

0032. A "carbonyl group’ as used herein refers to a carbon pressure at sea level. A psig of 30 represents an absolute
atom double-bonded to an oxygen atom (C=O). A carbonyl pressure of 44.7 psi (i.e., 30 plus atmospheric psi of 14.7), for
group can be located at either or both ends of the Cos example.
oxygenate; such a molecule could be referred to as an alde 0041. The terms “catalyst” and “metal catalyst” are used
hyde. Alternatively, one or more carbonyl groups can be interchangeably herein. The catalyst comprises a metal that
located within the carbonatom chain of the Cos oxygenate: increases the rate of Cos oxygenate hydrodeoxygenation
such a molecule could be referred to as a ketone. without itself being consumed or undergoing a chemical
0033. An “alcohol group’ as used herein refers to a carbon change. The catalyst is generally present in Small amounts
atom that is bonded to a “hydroxyl or “hydroxy” (OH) relative to the amounts of the reactants.
group. One or more alcohol groups can be located at any 0042. The terms “Periodic Table' and “Periodic Table of
carbon of the Co-s oxygenate (either or both ends, and/or the Elements' are used interchangeably herein.
one or more internal carbons of the Cos oxygenate carbon 0043. The terms “solid support”, “support', and “catalyst
chain). Support are used interchangeably herein. A solid Support
refers to the material to which an active metal is anchored.
0034. The terms “feedstock' and “feed are used inter Catalysts described herein that contain a Solid Support are
changeably herein. A feedstock refers to a material compris examples of 'supported metal catalysts’.
ing a saturated and/or unsaturated Cos oxygenate. A feed 0044) The terms “specific surface area”, “surface area'.
stock may be a “renewable' or “biorenewable' feedstock, and 'solid Support Surface area’ are used interchangeably
which refers to a material obtained from a biological or bio herein. The specific Surface area of a Solid Support is
logically derived source. expressed herein as square meters per gram of Solid Support
0035 Examples of such feedstock are materials contain (m/g). The specific Surface area of the Solid supports dis
ing monoglycerides, diglycerides, triglycerides, free fatty closed herein can be measured, for example, using the
acids, and/or combinations thereof, and include lipids such as Brunauer, Emmett and Teller (BET) method (Brunauer et al.,
fats and oils. These particular types offeedstocks, which can J. Am. Chem. Soc. 60:309-319; incorporated herein by refer
also be referred to as “oleaginous feedstocks, include animal ence).
fats, animal oils, poultry fats, poultry oils, plant and vegetable 0045. The terms “impregnation' and “loading are used
fats, plant and vegetable oils, yeast oils, rendered fats, ren interchangeably herein. Impregnation refers to the process of
dered oils, restaurant grease, brown grease, waste industrial rendering a metal salt into a finely divided form or layer on a
frying oils, fish oils, fish fats, and combinations thereof. For Solid Support. Generally, this process involves drying a mix
feedstocks comprising fat or oil, it would be understood by ture containing a solid Support and a metal salt solution. The
one of skill in the art that all or most of the Co-s oxygenate dried product can be referred to as a “pre-catalyst”.
is comprised in the feedstock in the form of an ester (fatty acid 0046. The terms “calcining and "calcination” as used
esterified to glycerol). Hydrodeoxygenation of Such Cos herein refer to a thermal treatment to convert the dried metal
oxygenates according to the disclosed process involves the salt of a pre-catalyst to a metallic or oxide state. The thermal
complete reduction of the ester group of the esterified fatty treatment can be performed in either an inert or active atmo
acid, which in part entails breaking the ester linkage between sphere.
the fatty acid and the glycerol molecule. 0047. The terms “molar yield”, “reaction yield', and
0036 Alternatively, a feedstock can refer to a petroleum "yield' are used interchangeably herein. Molar yield refers to
or fossil fuel-derived material comprising a saturated or the amount of a product obtained in a chemical reaction as
unsaturated Co-s oxygenate. measured on a molar basis. This amount can be expressed as
0037. The terms “fatty acid distillate” and “fatty acid dis a percentage; i.e., the percent amount of a particular product
tillate of an oil as used herein refer to a composition com in all of the reaction products.
prising the fatty acids of a particular type of oil. For example, 0048. The terms “reaction mix”, “reaction mixture', and
a palm fatty acid distillate comprises fatty acids that are “reaction composition' are used interchangeably herein. A
present in palm oil. Fatty acid distillates commonly are reaction mix can minimally comprise a feedstock (Substrate)
byproducts of plant oil refining processes. and catalyst. It may further comprise a solvent. A reaction mix
0038. The terms “moiety”, “chemical moiety”, “func can describe the mix as it exists before or during application
tional moiety', and “functional group' are used interchange of the temperature and pressure hydrodeoxygenation condi
tions.
ably herein. A moiety as used herein refers to a carbon group 0049 Disclosed herein is a hydrodeoxygenation process
comprising a carbon atom bonded to an oxygen atom.
Examples of a moiety as used herein include ester, carboxylic that can be carried out under conditions of low temperature
acid, carbonyl and alcohol groups. and pressure, and which converts Cos oxygenates in feed
stocks to linear alkanes without Substantial carbon loss.
0039. The terms “percent by weight”, “weight percentage Therefore, the process produces fewer undesirable by-prod
(wt %)' and “weight-weight percentage (% w/w) are used ucts and is more economical since it can be run under lower
interchangeably herein. Percent by weight refers to the per temperature and lower pressure conditions.
centage of a material on a mass basis as it is comprised in a 0050 Embodiments of the disclosed invention concern a
composition or mixture. For example, percent by weight hydrodeoxygenation process for producing a linear alkane
refers to the percentage of a metal by mass that is present in a from a feedstock comprising a saturated or unsaturated Cos
catalyst as described herein. Except as otherwise noted, all oxygenate that comprises a moiety selected from the group
the percentage amounts of metals disclosed herein refer to consisting of an ester group, carboxylic acid group, carbonyl
percent by weight of the metals in catalysts. group and alcohol group. This process comprises contacting
0040. As used herein, "psig (pound-force per square inch the feedstock with a catalyst comprising (i) about 0.1% to
gauge) refers to a unit of pressure relative to atmospheric about 10% by weight of a first metal selected from Group IB
US 2014/0081065 A1 Mar. 20, 2014

or VIII of the Periodic Table, and (ii) about 0.5% to about 15% 0056. The Cos oxygenate comprised in the feedstock
by weight of a second metal selected from the group consist may be a fatty acid or a triglyceride. The feedstock may
ing of tungsten, rhenium, molybdenum, Vanadium, manga comprise one or more fatty acids that are in the free form (i.e.,
nese, Zinc, chromium, germanium, tin, titanium, gold, and non-esterified) or that are esterified. Esterified fatty acids may
zirconium, at a temperature between about 150° C. to about be those comprised within a glyceride molecule (i.e., in a fat
250° C. and a hydrogen gas pressure of at least about 300 psig. or oil) or fatty acid alkyl ester (e.g., fatty acid methyl ester or
By contacting the feedstock with the catalyst under these fatty acid ethyl ester), for example. The fatty acid(s) may be
temperature and pressure conditions, the Cos oxygenate is saturated or unsaturated. Examples of unsaturated fatty acids
hydrodeoxygenated to a linear alkane that has the same car are monounsaturated fatty acids (MUFA) if only one double
bon chain length as the Cos oxygenate. Optionally, the bond is present in the fatty acid carbon chain, and polyun
hydrodeoxygenation process further comprises the step of saturated fatty acids (PUFA) if the fatty acid carbon chain has
recovering the linear alkane produced in the contacting step. two or more double bonds. The carbon chain length of a fatty
0051. The feedstock used in certain embodiments of the acid Cos oxygenate in the feedstock may be 10, 11, 12, 13.
disclosed invention may comprise a material comprising one 14, 15, 16, 17, or 18 carbon atoms. Preferably, the carbon
or more monoglycerides, diglycerides, triglycerides, free chain length is 10, 12, 14, 16, or 18 carbon atoms. Another
fatty acids, and/or combinations thereof, and include lipids preferred fatty acid length is 10-14 carbon atoms. Yet another
Such as fats and oils. Examples of such feedstocks include fats preferred fatty acid length is 16-18 carbon atoms. Examples
and/or oil derived from animals, poultry, fish, plants, offatty acids that can be in the feedstock are provided in Table
microbes, yeast, fungi, bacteria, algae, euglenoids and/or 1.
stramenopiles. Examples of plant oils include canola oil, corn
oil, palm kernel oil, cheru seed oil, wild apricot seed oil, TABLE 1
sesame oil, Sorghum oil, soy oil, rapeseed oil, soybean oil, Examples of Saturated and Unsaturated Fatty Acids
colza oil, tall oil, sunflower oil, hempseed oil, olive oil, lin that May Be Comprised in Feedstocks
seed oil, coconut oil, castor oil, peanut oil, palm oil, mustard
oil, cottonseed oil, camelina oil, jatropha oil and crambe oil. Shorthand
Common Name Chemical Name Notation
Other feedstocks include, for example, rendered fats and oil,
restaurant grease, yellow and brown greases, waste industrial Capric decanoic O:O
frying oil, tallow, lard, train oil, fats in milk, fish oil, algal oil, Undecylic undecanoic 1:O
Lauric dodecanoic 2:O
yeast oil, microbial oil, yeast biomass, microbial biomass, Tridecylic tridecanoic 3:O
sewage sludge and Soap stock. Myristic tetradecanoic 4:O
Myristoleic tetradecenoic 4:1
0052 Derivatives of oils such as fatty acid distillates are pentadecylic pentadecanoic 5:0
other examples of feedstocks that can be used in certain Palmitic hexadecanoic 6:O
embodiments of the invention. Plant oil distillates (e.g., palm Palmitoleic 9-hexadecenoic 6:1
fatty acid distillate) are preferred examples of fatty acid dis Margaric
hexadecadienoic
heptadecanoic
6:2
7:0
tillates. A fatty acid distillate of any of the fats and oils Stearic octadecanoic 8:0
disclosed herein may be used in the invention. Oleic cis-9-octadecenoic 8:1
0053. The feedstock comprises a plant oil or a fatty acid Linoleic
gamma-linolenic
cis-9,12-octadecadienoic
cis-69,12-
8:2 omega-6
8:3 omega-6
distillate thereof in a preferred embodiment of the invention. octadecatrienoic
In another preferred embodiment, the feedstock comprises (i) alpha-linolenic cis-9,12,15- 8:3 omega-3
a plant oil selected from the group consisting of Soybean oil, octadecatrienoic
palm oil and palm kernel oil; or (ii) a palm fatty acid distillate. Stearidonic cis-69,12,15-
octadecatetraenoic
8:4 omega-3
Palm oil is derived from the mesocarp (pulp) of the fruit of the
oil palm, whereas palm kernel oil is derived from the kernel of
the oil palm. The fatty acids comprised in palm oil typically 0057 Although the oxygenates comprised in the feed
include palmitic acid (~.44%), oleic acid (-37%), linoleic acid stocks used in the disclosed invention have a length of 10-18
(~9%), stearic acid and myristic acid. The fatty acids com carbon atoms, other oxygenates with a carbon length outside
prised in palm kernel oil typically include lauric acid (~48%), this range may also be present in the feedstock. For example,
myristic acid (~16%), palmitic acid (-8%), oleic acid the glycerides and free fatty acids of the fats and oils that can
(~15%), capric acid, caprylic acid, Stearic acid and linoleic be used as feedstock may also contain carbon chains of about
acid. Soybean oil typically comprises linoleic acid (-55%). 8 to 24 carbon atoms in length. In other words, the feedstock
palmitic acid (~11%), oleic acid (-23%), linolenic acid and need not comprise only Cols Oxygenates.
Stearic acid.
0058. The Co. oxygenates represented by lipids and
0054 Fossil fuel-derived and other types of feedstocks free fatty acids comprise ester and carboxylic acid moieties,
that can be used in certain embodiments of the disclosed respectively. Other types of Cos oxygenates may be com
invention include petroleum-based products, spent motor oils prised in the feedstock Such as those Cos oxygenates con
and industrial lubricants, used paraffin waxes, coal-derived taining one or more carbonyl and/or alcohol moieties. Still
liquids, liquids derived from depolymerization of plastics other types of Cos oxygenates may contain two or more of
Such as polypropylene, high density polyethylene, and low any of the above moieties. Examples include Cos oxygen
density polyethylene; and other synthetic oils generated as ates comprising two or more alcohol moieties (e.g., diols),
byproducts from petrochemical and chemical processes. carbonyl moieties (e.g., diketones or dialdehydes), carboxy
0055 Examples of other feedstocks that can be used lic acid moieties (dicarboxylic acids), or ester moieties (di
herein are described in U.S. Pat. Appl. Publ. No. 2011 esters). Co-s oxygenates comprising alcohol and carbonyl
0300594, which is incorporated herein by reference. moieties (e.g., hydroxyketones and hydroxyaldehydes), alco
US 2014/0081065 A1 Mar. 20, 2014

hol and carboxylic acid moieties (e.g., hydroxycarboxylic example. The feedstock in certain embodiments may com
acids), alcohol and ester moieties (e.g., hydroxyesters), car prise any of these various C oxygenates. For example, the
bonyl and carboxylic acid moieties (e.g., keto acids), or car feedstock may be an oil or fat comprising palmitic acid (i.e.,
bonyl and ester moieties (e.g., keto esters) are other example contain a palmitoyl group) or palmitoleic acid (i.e., contain a
components offeedstocks that can be used in embodiments of 9-hexadecenoyl group).
the disclosed invention. 0065 Octadecane is a linear alkane that can be produced
0059. The feedstock may contain one or more Cos oxy by the disclosed hydrodeoxygenation process. Various Cs
genates linked together by two or more ester and/or ether oxygenates can be used as feedstock to produce octadecane,
linkages. Such Cols oxygenates are unlinked from each including octadecanol (e.g., Stearyl alcohol), octadecyl alde
other during the disclosed hydrodeoxygenation process; the hyde, octadecyl ketone, Stearic acid, Stearyl Stearate, and/or
removal of oxygen from Such molecules destroys the ester any other Cs oxygenate in which one or more carbon atoms
and/or ether linkages. Similarly, the fatty acid Cos oxygen of the C18 chain are bonded to an oxygenatom, for example.
ates as contained in a glyceride feedstock are unlinked from The feedstock in certain embodiments may comprise any of
the glycerol component of the glyceride during the disclosed these various Cs oxygenates. For example, the feedstock
hydrodeoxygenation process since the fatty acid ester link may be an oil or fat comprising Stearic acid (i.e., contain a
ages are destroyed by the removal of oxygen. Therefore, Stearoyl group), oleic acid (i.e., contain a 9-octadecenoyl
different types of linear alkanes can be produced from feed group), or linoleic acid (i.e., contain a 9, 12-octadecadienoyl
stocks containing two or more different Cos oxygenates, group).
even if the Cos oxygenates are linked by ester and/or ether 0066. The molar yield of the linear alkane is at least about
linkages. All these types of Cos oxygenates may be con 25% in certain embodiments of the disclosed invention. In
stituent components of the feedstock. other embodiments, the molar yield of the linear alkane is at
0060. The linear chain of the Cos oxygenate is not least about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%,
linked to any alkyl or aryl branches via a carbon-carbon bond 19%. 20%, 21%, 22%, 23%, 24%, 26%, 27%, 28%, 29%,
from one of the carbonatoms of the linear chain. For example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%,
while lauric acid is a Cos oxygenate in certain embodi 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%,
ments, lauric acid having an alkyl group Substitution (e.g., 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%,
11-methyl lauric acid) at one of its —CH2— moieties is not a 60%, 61%. 62%, 63%, 64%. 65%, 66%, 67%, 68%, 69%,
type of Cos oxygenate as described herein. The disclosed 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%,
hydrodeoxygenation process does not involve isomerization 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%,
events that involve removing and/or adding carbon-carbon 90%, 91%, 92%, 93%, 94%, or 95%. For example, where
bonds. Therefore, branched alkane products such as isode lauric acid is the Co-oxygenate comprised in the feedstock
canes, isododecanes, isotetradecanes, isohexadecanes and for the process, the molar yield of dodecane is at least about
isooctadecanes are not produced. 25%.
0061 The Cos oxygenate may constitute the feedstock 0067. The carbon chain length of the linear alkane product
itself in certain embodiments of the disclosed invention. An of the disclosed hydrodeoxygenation process is the same
example of Such a feedstock is a pure or Substantially pure carbon chain length of the Cos oxygenate. For example, if
preparation of a particular fatty acid. Alternatively, the feed the Cos oxygenate is lauric acid, the resulting linear alkane
Stock may comprise multiple separate Cos Oxygenates (i.e., is dodecane (both lauric acid and dodecane have a carbon
distinct molecules that are not linked to each other). Mixtures chain length of twelve carbon atoms). As another example, if
of any of the above feedstocks may be used as co-feed com the Cos oxygenate is palmitic acid, the resulting linear
ponents in the disclosed hydrodeoxygenation process. alkane is hexadecane (both palmitic acid and hexadecane
0062. A linear alkane is produced from a saturated or have a carbon chain length of sixteen carbon atoms). The
unsaturated Co- oxygenate in the disclosed hydrodeoxy linear alkane produced in the disclosed process therefore
genation process. The linear alkanes produced in certain represents the completely hydrogen-saturated, reduced form
embodiments include decane, undecane, dodecane, tride of the Cos oxygenate in the feedstock. For example, the
cane, tetradecane, pentadecane, hexadecane, heptadecane disclosed hydrodeoxygenation process produces decane
and octadecane, where those of these linear alkanes having an from capric acid; dodecane from lauric acid; tetradecane from
even carbon atom number are produced in preferred embodi myristic acid and myristoleic acid; hexadecane from palmitic
mentS. acid and palmitoleic acid; and octadecane from Stearic acid,
0063. As disclosed above, dodecane is the linear alkane oleic acid and linoleic acid. These linear alkanes are produced
produced in certain embodiments of the disclosed hydrode whether the fatty acids are free oresterified. A Co. oxygen
oxygenation process. Various C oxygenates can be used as ate that is linked to one or more other components via ester
feedstock to produce dodecane, including dodecanol, dode and/or ether linkages yields a linear alkane during the dis
cylaldehyde, dodecyl ketone, lauric acid, lauryl laurate, and/ closed process that represents the completely hydrogen-satu
or any other C. oxygenate in which one or more carbon rated, reduced form of the Cos oxygenate.
atoms of the C12 chain are bonded to an oxygen atom, for 0068. In certain embodiments of the disclosed invention,
example. the molar yield is less than about 10% for a reaction product
0064. Hexadecane is a linear alkane that can be produced having a carbon chain length that is one or more carbonatoms
by the disclosed hydrodeoxygenation process. Various C. shorter than the carbon chain length of the Cos oxygenate.
oxygenates can be used as feedstock to produce hexadecane, For example, where lauric acid is the Cos oxygenate com
including hexadecanol (e.g., cetyl alcohol), hexadecyl alde prised in the feedstock for the process, the molar yield of
hyde, hexadecyl ketone, palmitic acid, palmityl palmitate, undecane which has a chain length of eleven carbonatoms is
and/or any other C oxygenate in which one or more carbon less than about 10%. In other embodiments, the molar yield is
atoms of the C16 chain are bonded to an oxygen atom, for less than about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9% for
US 2014/0081065 A1 Mar. 20, 2014

a reaction product having a carbon chain length that is one or or more reactors in series. Fresh hydrogen may be added at the
more carbonatoms shorter than the carbon chain length of the inlet of each reactor in this type of system. A recycle stream
Cos oxygenate. The low level of Such byproducts using the may also be used to help maintain the desired temperature in
disclosed invention reflects a low level of carbon loss from the each reactor. The reactor temperature may also be controlled
Cos oxygenate by decarboxylation and/or decarbonylation by controlling the fresh feedstock temperature and the recycle
events during the hydrodeoxygenation reaction. Therefore, rate.
the disclosed process does not significantly break carbon 0075. In certain embodiments, the contacting step may
carbon bonds of the Cos oxygenate. comprise agitating or mixing the feedstock and catalyst
0069. The molar yield of other types of byproducts in before and/or while the reaction components are subjected to
certain embodiments of the disclosed invention is less than the above temperature and hydrogen gas pressure conditions.
about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, Agitation can be performed using a mechanical stirrer, or in a
12%, 13%, 14%, or 15%. Such other byproducts include slurry reactor system, for example.
products that represent incompletely reduced forms of the 0076. The contacting step in certain embodiments may be
Co. oxygenate that retain one or more oxygenated carbon performed in a solvent, such as an organic solvent or water.
atoms (e.g., alcohol group, carbonyl group, carboxylic acid The solvent may consist of one type of solvent that is pure or
group, ester group), and/or one or more points of unsatura substantially pure (e.g., >99% or >99.9% pure) or comprise
tion. Examples of byproducts include dodecanol and lauryl two or more different solvents mixed together. The solvent
laurate when using lauric acid in the feedstock. may be homogeneous (e.g., single-phase) or heterogeneous
0070 The disclosed hydrodeoxygenation process can be (e.g., two or more phases). In a preferred embodiment, the
tested, for example, with respect to its ability to convert lauric feedstock and the catalyst are contacted in an organic solvent.
acid or dodecanol into dodecane. In other words, a hydrode The organic Solvent used in certain embodiments may be
oxygenation process for converting any Co-s oxygenate to non-polar or polar. The organic solvent comprises tetrade
an alkane can be tested using lauric acid or dodecanol as the cane, hexadecane, or dodecane in another embodiment. Alter
feedstock; such processes when tested on lauric acid or dode natively, the organic solvent may be another alkane Such as
canol can have molar yields of dodecane as listed above for one having a chain length of 6 to 18 carbon atoms. The
linear alkanes. Similarly, such processes when tested on lau organic solvent may be selected on the basis of its ability to
ric acid or dodecanol can have molaryields of byproducts less dissolve hydrogen. For example, the solvent can have a rela
than about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, tively high solubility for hydrogen so that substantially all the
11%, 12%, 13%, 14%, or 15%. hydrogen provided by the hydrogen gas pressure is in solution
0071. The linear alkanes produced in the disclosed process before and/or during the disclosed hydrodeoxygenation pro
can be isolated by any means known in the art Such as close cess. The ratio of solvent to feedstock substrate on a weight
cut distillation, for example. If necessary, selective adsorp basis (e.g., grams) can be between about 1:1 to 15:1, and
tion with molecular sieves can be used to further purify the preferably is between about 2:1 to 10:1.
linear alkanes from those reaction byproducts that are bulkier 0077. The solvent can be tetradecane, hexadecane, or a
than the linear alkanes. Molecular sieves can comprise Syn mixture thereof, for example. Certain embodiments of the
thetic Zeolites having a series of central cavities intercon invention use a solvent comprising tetradecane and hexade
nected by pores. The pores have diameters large enough to cane. Examples of such a solvent have a tetradecane-to-hexa
permit passage of linear alkanes, but not large enough to decane ratio of about 15:1, 16:1, 17:1, 18:1, 19:1, or 20:1,
allow passage of branched byproducts. Commercial isolation where the ratio is determined on a weight basis (e.g., grams).
processes using molecular sieves include IsoSivTM (Dow A ratio of about 17:1 tetradecane-to-hexadecane is preferred
Chemical Company), MolexTM (UOP LLC) and EnsorbTM in certain embodiments. Solvents having these relative
(ExxonMobil Corporation), for example. amounts of tetradecane and hexadecane are capable of
0072 The disclosed invention includes the step of contact enhancing product yields in certain of the hydrodeoxygen
ing the feedstock comprising a Co-s oxygenate with a cata ation reactions disclosed herein. These ratios can characterize
lyst at a temperature between about 150° C. to about 250° C. the initial solvent conditions of the hydrodeoxygenation reac
and a hydrogen gas pressure of at least about 300 psi.g. tions (e.g., the reaction conditions just after all the reaction
0073. The step of contacting the feedstock with the cata components have been added, and/or before application of
lyst may be performed in a reaction vessel or any other enclo elevated temperature and pressure conditions).
Sure known in the art that allows performing a reaction under 0078. The contacting step of the disclosed process is per
controlled temperature and pressure conditions. For example, formed at a temperature between about 150° C. to about 250°
the contacting step is performed in a packed bed reactor, Such C. and a hydrogen gas pressure of at least about 300 psig. The
as a plug flow, tubular or other fixed bed reactor. It should be temperature in certain embodiments may be about 150° C.
understood that the packed bed reactor may be a single 160° C. 170° C., 180°C., 190° C., 200° C., 210°C., 220°C.,
packed bed or comprise multiple beds in series and/or in 230°C.,240°C., or 250° C. Alternatively, the temperature is
parallel. Alternatively, the contacting step can be performed between about 150° C. to about 200° C. The temperature is
in a slurry reactor, including batch reactors, continuously about 200° C. and the pressure is about 400 psig in other
stirred tank reactors, and/or bubble column reactors. In slurry embodiments of the disclosed invention. The hydrogen gas
reactors, the catalyst may be removed from the reaction mix pressure in certain embodiments may be between about 300
ture by filtration or centrifugal action. The size/volume of the psig to about 1000 psig, about 300 psig to about 500 psig,
reaction vessel should be suitable for handling the chosen between about 350 psig to about 450 psig, or at about 400
amount of feedstock and catalyst. psig.
0074 The contacting step may be performed in any con 007.9 The feedstock and catalyst can be contacted in any
tinuous or batch processing system as known in the art. A of the above temperature and hydrogen pressure conditions
continuous process may be multi-stage using a series of two for about 2,3,4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
US 2014/0081065 A1 Mar. 20, 2014

19 or 20 hours. Alternatively, the feedstock and catalyst can weight of platinum as the first metal and about 2% to about
be subjected to any of the above temperature and hydrogen 10% by weight of tungsten as the second metal. Thus, in
pressure conditions for a continuous period of time. certain embodiments of the invention, the catalyst comprises
0080. In certain embodiments, the feedstock is contacted about 2.0% by weight of platinum as the first metal and about
with hydrogen to form a feedstock/hydrogen mixture in 2%, about 5%, about 7.5%, or about 10% by weight of tung
advance of contacting the feedstock with the catalyst. In other Sten as the second metal.
embodiments, a solvent or diluent is added to the feedstock in I0086. The catalyst comprises platinum as the first metal
advance of contacting the feedstock with hydrogen and/or and molybdenum as the second metal in other embodiments
catalyst. For example, after forming a feedstock/solvent mix of the invention. An example of Such a catalyst comprises
ture, it may then be contacted with hydrogen to form a feed about 1.5% to about 2.5% by weight of platinum and about
stock/solvent/hydrogen mixture which is then contacted with 1.5% to about 2.5% by weight of molybdenum. Another
the catalyst. example of Such a catalyst comprises about 2% by weight of
0081. A wide range of suitable catalyst concentrations platinum and about 2% by weight of molybdenum.
may be used in the disclosed process, where the amount of I0087. The catalyst further comprises a solid support in
catalyst per reactoris generally dependent on the reactor type. certain embodiments of the disclosed invention. Various solid
For a fixed bed reactor, the volume of catalyst per reactor will Supports as known in the art can be comprised in the catalyst,
be high, while in a slurry reactor, the volume will be lower. including one or more of WOs, Al-O (alumina), TiO, (tita
Typically, in a slurry reactor, the catalyst will make up 0.1 to nia), TiO, Al2O, ZrO tungstated ZrO, SiO, SiO
about 30 wt % of the reactor contents. Al-O, SiO, TiO, VOs, Mo.O. or carbon, for example. In
0082. The disclosed invention includes the step of contact a preferred embodiment, the Solid Support comprises Al2O.
ing the feedstock comprising a Co-s oxygenate with a cata The Solid Support may therefore comprise an inorganic oxide,
lyst comprising (i) about 0.1% to about 10% by weight of a metal oxide or carbon. Other examples of solid supports that
first metal selected from Group IB or VIII of the Periodic may be used include clay (e.g., montmorillonite) and Zeolite
Table, and (ii) about 0.5% to about 15% by weight of a second (e.g., H-Y Zeolite). The Support material used in the catalyst
metal selected from the group consisting of tungsten, rhe such as those described above may be basic (pH 9.5), neu
nium, molybdenum, Vanadium, manganese, Zinc, chromium, tral, weakly acidic (pH between 4.5 and 7.0), or acidic (spH
germanium, tin, titanium, gold and Zirconium. Thus, the first 4.5). Additional examples of solid Supports that can be used in
metal may be copper, silver, or gold, which are Group IB certain embodiments of the disclosed invention are described
metals; or iron, ruthenium, osmium, cobalt, rhodium, iridium, in U.S. Pat. No. 7,749,373 which is herein incorporated by
nickel, palladium, or platinum, which are Group VIII metals. reference.
In certain preferred embodiments, the first metal is one or I0088. The solid support used in certain embodiments of
more of platinum, copper, nickel, palladium, rhodium, or the disclosed invention may be porous, thereby increasing the
iridium. Surface area onto which the metal catalyst is attached. In
0083. The catalyst in certain embodiments may comprise certain preferred embodiments, the Solid Support comprises
about 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, pores and has (i) a specific surface area that is at least 10 m/g
4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, and optionally less than or equal to 280 m/g, wherein the
8.5%, 9.0%, 9.5% or 10% by weight of one or more of any of pores have a diameter greater than 500 angstroms and the
the above first metals, and about 0.5%, 1.0%, 1.5%, 2.0%, pore volume of the support is at least 10 ml/100 g; or (ii) a
2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, specific surface area that is at least 50 m/g and optionally less
7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 10.5%, 11.0%, than or equal to 280 m/g, wherein the pores have a diameter
11.5%, 12.0%, 12.5%, 13.0%, 13.5%, 14.0%, 14.5%, or greater than 70 angstroms and the pore Volume of the Support
15.0% by weight of one or more of any of the above second is at least 30 ml/100 g.
metals. The first metal and the second metal are different; I0089. Thus, the specific surface area of the solid support
therefore the catalyst has at least two different metals. In can be about or at least about 10, 20, 30, 40, 50, 60, 70, 80,90,
certain embodiments, the catalyst comprises no more than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210,
two or three different metals. 220, 230, 240,250, 260,270, or 280 m/g. The solid support
0084. The catalyst can comprise platinum as the first metal has a specific surface area of about 150 m/g to about 200
and tungsten as the second metal, for example. In a preferred m/gin another embodiment, while in other embodiments it is
embodiment, the catalyst comprises about 4% to about 6% by about 170 to 190 m/g, or about 175 to 185 m/g. Preparing a
weight of platinum as the first metal and about 1.5% to about porous solid Support with a particular specific Surface area
2.5% by weight of tungsten as the second metal. Such a can be performed by modulating pore diameter and Volume as
catalyst may comprise about 4.0%, 4.25%, 4.5%, 4.75%, known in the art (e.g., Trimm and Stanislaus, Applied Cataly
5.0%, 5.25%, 5.5%, 5.75%, or 6.0% by weight of platinum, sis 21:215-238; Kim et al., Mater. Res. Bull. 39:2103-2112:
and about 1.5%, 1.75%, 2.0%, 2.25%, or 2.5% by weight of Grant and Jaroniec, J. Mater: Chem. 22:86-92).
tungsten. The catalyst in another preferred embodiment com 0090 The solid support in certain embodiments may have
prises about 5% by weight of platinum as the first metal and a mean particle size of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or
about 2% by weight of tungsten as the second metal. 15 microns. In a preferred embodiment, the mean particle size
0085. In other embodiments, the catalyst comprises about is about 10 microns.
1% to about 6% by weight of platinum as the first metal and 0091 Solid supports for preparing the catalysts used in
about 1.5% to about 15% by weight oftungsten as the second certain embodiments of the disclosed invention are available
metal. Alternatively, the catalyst may comprise about 1.5% to from a number of commercial Sources, including Johnson
about 2.5% by weight of platinum as the first metal and about Matthey, Inc. (West Deptford, N.J.), BASF (Iselin, N.J.),
2% to about 10% by weight oftungsten as the second metal. Evonik (Calvert City, Ky.) and Sigma-Aldrich (St. Louis,
Still alternatively, the catalyst may comprise about 2.0% by Mo.), for example. Regarding Support materials from
US 2014/0081065 A1 Mar. 20, 2014

Johnson Matthey (JM), alumina particles designated #32 (JM metal salt Solution, drying this mixture as above, mixing the
32) have a mean particle size of 10 microns and a Surface area dried product with another metal salt Solution, drying this
of 300 m/g, and alumina particles designated #33 (JM 33) mixture as above, and then calcining the dried product as
have a mean particle size of 15 microns and a Surface area of above. Either of the above procedures can be adapted accord
180 m/g. ingly to load additional metals onto the Solid Support.
0092. The catalyst in certain embodiments can be in the 0097 Metal-comprising salts known in the art to be useful
form of particles such as shaped particles. Catalyst particles in preparing Supported metal catalysts can be used to prepare
can be shaped as cylinders, pellets, spheres, or any other the catalyst following an impregnation-calcining procedure.
shape. Cylinder-shaped catalysts may have hollow interiors, Examples of Such useful salts include nitrates, halides (e.g.,
with or without one or more reinforcing ribs. Other particle chloride, bromide), acetates and carbonates. Ammonium
shapes that may be used include trilobe, cloverleaf, cross, tungstate pentahydrate (NF).W.O.5H2O and tet
"C'-shaped, rectangular- and triangular-shaped tubes, for raamine platinum nitrate (NH). Pt(NO) (also commonly
example. Alternatively, the catalyst may be in the form of referred to as tetraamine platinum dinitrate) are examples of
powder or larger sized cylinders or tablets. tungsten and platinum salts, respectively, that can be used to
0093. Other examples of metal catalyst compositions that prepare the catalyst of the disclosed process.
can be used in certain embodiments of the disclosed invention 0098. The linear alkanes produced by the disclosed inven
are described in U.S. Pat. Appl. Publ. Nos. 2011-0300594 and tion are suitable for use in producing long-chain diacids by
2012-0029250, and U.S. Pat. No. 8,084,655, all of which are fermentation. For example, the linear alkanes may be fer
incorporated herein by reference. mented, individually or in combination, to linear dicarboxylic
0094. The catalyst can be prepared using any of a variety acids of 10 (decanedioic acid), 12 (dodecanedioic acid), 14
of ways known in the art (e.g., Pinna, 1998, Catalysis Today (tetradecanedioic acid), 16 (hexadecanedioic acid), or 18 (oc
41:129-137, Catalyst Preparation: Science and Engineering, tadecanedioic acid) carbons in length. Methods and microor
Ed. John Regalbuto, Boca Raton, Fla.: CRC Press, 2006; Mul ganisms for fermenting linear alkanes to linear dicarboxylic
and Moulijn, Chapter 1: Preparation of supported metal cata acids are described, for example, in U.S. Pat. Nos. 5.254.466;
lysts, In: Supported Metals in Catalysis, 2nd Edition, Eds. J. 5,620,878; 5,648,247, and U.S. Pat. Appl. Publ. Nos. 2011
A. Anderson and M. F. Garcia, London, UK: Imperial College 0300594, 2005-0181491 and 2004-0146999 (all of which are
Press, 2011, Acres et al., The design and preparation of Sup incorporated herein by reference). Methods for recovering
ported catalysts, In: Catalysis. A Specialist Periodical linear dicarboxylic acids from fermentation broth are also
Report, Eds. D. A. Dowden and C. C. Kembell, London, UK: known, as disclosed in some of the above references and also
The Royal Society of Chemistry, 1981, Vol. 4, pp. 1-30). It is in U.S. Pat. No. 6,288,275 and International Pat. Appl. Publ.
desirable that the catalyst prepared by a chosen method be No. WO2OOO-O2O62O.
active, selective, recyclable, and mechanically and thermo
chemically stable during the disclosed hydrodeoxygenation EXAMPLES
process.
0099. The disclosed invention is further defined in the
0095. The catalyst used in certain embodiments of the following Examples. It should be understood that these
disclosed invention may be prepared through sequential Examples, while indicating preferred aspects of the inven
impregnation of a solid Support with the metals used herein tion, are given by way of illustration only. From the above
(i.e., one or more of a Group IB or VIII metal of the Periodic discussion and these Examples, one skilled in the art can
Table, and one or more of tungsten, rhenium, molybdenum, ascertain the essential characteristics of this invention, and
Vanadium, manganese, Zinc, chromium, germanium, tin, tita without departing from the spirit and scope thereof, can make
nium, gold, or Zirconium). For example, in preparing Sup various changes and modifications of the invention to adapt it
ported metal catalysts comprising platinum and tungsten, to various uses and conditions.
platinum may be impregnated onto the Solid Support first to
form a platinum-Supported catalyst, which is then impreg Example 1
nated with tungsten. Tungsten can be impregnated onto the
Support first followed by platinum impregnation in another Catalyst Synthesis: 2% Tungsten/5% Platinum on
example. Optionally, reduction and passivation steps can be Al-O
applied following the first impregnation and before the sec
ond impregnation. In certain embodiments, a metal can be 0100. This Example describes the impregnation of tung
impregnated onto a Supported metal catalyst obtained from a Sten (W) on an alumina (AlO)-supported platinum (Pt)
commercial source. Alternatively, each of the selected metals catalyst. The resulting alumina-Supported tungsten/platinum
can be impregnated onto the Solid Support at the same time, catalyst was used in the low temperature/low pressure hydro
without sequential impregnation. deoxygenation processes described in Examples 2 and 3.
0096. The impregnation of each metal onto the solid Sup 0101 Two wt % tungsten was loaded on a 5 wt % alumina
port in preparing certain catalysts for use in the disclosed Supported platinum catalyst (Pt/Al2O) using a wet impreg
process may be performed by mixing the Solid Support with a nation method. To achieve tungsten impregnation on the Sup
metal salt solution, drying this mixture at a suitable tempera port, 0.083 g of ammonium tungstate pentahydrate (Strem
ture (e.g., 100 to 120° C.) for a suitable amount of time to Chemicals, Newburyport, Mass.: lot no. 19424200) was dis
obtain a dried product, and then calcining the dried product at solved in 2 mL of deionized water. This solution was then
a suitable temperature (e.g., 300 to 400° C.) for a suitable added to 2.92 g of dry alumina-Supported 5% platinum cata
amount of time. The Supported metal catalyst prepared by this lyst (Pt/Al2O) powder from Johnson Matthey, Inc. (West
procedure may then be impregnated with another metal. Deptford, N.J.; JM #33 alumina support). This Pt/Al2O pow
Alternatively, the impregnation of each metal onto the Solid der has a moisture content of 1%, uniform metal location, a
Support may be performed by mixing the solid Support with a surface area of 180 m/g, a mean particle size of 15 microns,
US 2014/0081065 A1 Mar. 20, 2014

and a nitrobenzene activity of 200 mL H/15 min. The mix 0108. With respect to the final product of the reaction, the
ture-solution was vortexed for about 5 minutes. The sample conversion of lauric acid was observed to be about 95%, while
was then dried overnight for about 16 hours in a vacuum oven the molar yield of dodecane was about 65%. The molar yield
at 110° C. under a vacuum of 20 mm Hg. A small nitrogen was about 12% for dodecanol, about 11% for lauryl laurate,
bleed was used to assist in the removal of water vapor during and about 2% for undecane.
this drying process. The sample was then cooled to room 0109 These results demonstrate that a feedstock compris
temperature before calcining it for 3 hours at 350° C. ing the C2 oxygenate, lauric acid, can be used to produce a
0102 Thus, a 2% tungsten/5% platinum alumina-Sup linear alkane via a hydrodeoxygenation process that employs
ported catalyst was obtained. a W/Pt/alumina catalyst under conditions of low temperature
and pressure. The hydrodeoxygenation process mostly pro
Example 2 duced a completely deoxygenated product (dodecane) with a
Small amount of certain by-products.
Selective Hydrodeoxygenation of Lauric Acid to I0110 Specifically, the low production of undecane (C)
Dodecane in a 600-cc Reactor demonstrates that only a very low level of carbon loss through
lauric acid decarboxylation occurred during the process. The
0103) This Example describes the selective hydrodeoxy high level of dodecane produced with a relatively low amount
genation of lauric acid to dodecane using the alumina-Sup of the side products dodecanol and lauryl laurate demon
ported tungsten/platinum catalyst prepared in Example 1 (2% strates that the process efficaciously deoxygenated the car
W on 5% Pt/alumina). This process was carried out under boxylic acid moiety of the lauric acid feedstock.
conditions including a temperature of 200° C. and a pressure
of 500 psig (pound-force per square inch gauge). Example 3
0104 30.5g of lauric acid (Sigma Aldrich, St. Louis, Mo.; 0111 Selective Hydrodeoxygenation of Lauric Acid to
>99%, lot. no. MKBG4553V), 253.0 g of tetradecane (Alfa Dodecane in a 20-cc Multi-Reactor System
Aesar, Ward Hill, Mass.: 99.4%, lot. no. E09Y007), 15.3 g of 0112 This Example describes the selective hydrodeoxy
hexadecane (Sigma Aldrich, 99.9%, lot. no. 26396JMV) and genation of lauric acid to dodecane using the alumina-Sup
3.19 g of the alumina-Supported tungsten/platinum catalyst ported tungsten/platinum catalyst prepared in Example 1 (2%
prepared in Example 1 were added to a 600-cc Hastelloy W on 5% Pt/alumina). This process was carried out under
Parr R. pressure reactor equipped with a mechanical stirrer. conditions including a temperature of 200° C. and a pressure
The mechanical stirrer was set to a rotation speed of 700 rpm. of 400 psi.g.
The reactor was purged with nitrogen gas six times by pres 0113. The hydrodeoxygenation reaction was performed in
Surizing the reactor to about 400 psig each time and then an Endeavor R reactor System containing eight stainless steel
depressurizing it. The reactor was then purged with hydrogen reaction vessels. Each vessel has a volume of about 25 mL
gas six times by pressurizing the reactor to 200 psig and then and is equipped with mechanical stirring. A 20-mL glass vial
depressurizing it. is used as a liner for each reactor in this system.
0105. After these purging cycles, the reactor was pressur 0114 0.20 g of lauric acid (Sigma Aldrich, >99%, lot. no.
ized to about 100 psig of hydrogen and heated to 200°C. Once MKBG4553V), 1.71 g of tetradecane (Alfa Aesar, 99.4%, lot.
the reactor was equilibrated at 200° C., the reactor pressure no. E09Y007), 0.10g of hexadecane (Sigma Aldrich, 99.9%,
was raised to the experimental set point of 500 psig. A sample lot. no. 26396JMV) and 0.10 g of the alumina-supported
of the above input material (lauric acid with tetradecane, tungsten/platinum catalyst prepared in Example 1 were added
hexadecane and the W/Pt catalyst) was collected through a to a 20-mL glass vial used in one of the reaction vessels in the
sample port immediately after the reaction conditions (200° Endeavor R reaction system. The system was sealed and con
C. and 500 psig) were reached. Additional samples were nected to a high pressure gas manifold. The reactor was
collected every hour for the next five hours. After 6 hours at purged with nitrogen gas four times by pressurizing the reac
200° C., the reactor was allowed to cool down to 50° C. and tor to 400 psig each time and then depressurizing it. The
was held under those conditions overnight. reactor was then purged with hydrogen gas three times by
0106 The reactor was reheated again to 200° C. the fol pressurizing the reactor to 400 psig and then depressurizing it.
lowing day and the hydrogen pressure was adjusted to 500 0.115. After the purging cycles, the reactor was pressurized
psig. Again, a sample was collected immediately after the to 100 psig of hydrogen and heated to 200° C. Once the
reaction conditions (200° C. and 500 psig) were reached and reactor temperature reached 200° C., more hydrogen was
every hourthereafter for the next six hours. After 6 hours, the added to the reactor to raise its pressure to the experimental
reactor was allowed to cool down to room temperature and set point of 400 psig. The reaction was carried out isother
was depressurized to ambient pressure before dismantling it mally for four hours before switching off the heat and cooling
and collecting the reaction mixture. the reactor down to below 50° C. For the entire length of the
0107 All the collected samples were diluted with tetrahy reaction, the pressure was maintained at the 400 psig set point
drofuran and filtered through a standard 0.45-micron dispos by adding hydrogen whenever the pressure dropped below
able filter. The filtered samples were then analyzed by a 399 psig.
GC/FID (gas chromatography/flame ionization detector) to 0116. After the reactor was cooled down, the glass vial
identify the components thereof and to measure the concen used for the reaction was removed from the reactor and cen
trations of the reactants and products. The individual compo trifuged at 2000 rpm for 5 minutes. The resulting sample was
nents were identified by matching the retention times of the decanted off to separate the catalyst (solid sample) from the
components with those of certain calibration standards. The rest of the reaction mixture (liquid sample). The liquid sample
hexadecane that was included in the reaction was used as an was further diluted with tetrahydrofuran and filtered through
internal standard to determine the concentrations of each of a standard 0.45-micron disposable filter. The filtered liquid
the individual components. sample was then analyzed by a GC/FID to identify the com
US 2014/0081065 A1 Mar. 20, 2014

ponents thereof and to measure the concentrations of the TABLE 2-continued

reactants and products. The individual components were
identified by matching the retention times of the components Molar Selectivity and Molar Yield of Dodecane and Undecane
with those of certain calibration standards. The hexadecane from the Conversion of Lauric Acid Using Various Catalysts
that was included in the reaction was used as an internal Dodecane
standard to determine the concentrations of each of the indi
vidual components. Lauric Acid Selec- Undecane
0117. With respect to the final product of the reaction, the Catalyst Conversion tivity. Yield Selectivity. Yield
conversion of lauric acid was observed to be about 99%, while
the molar yield of dodecane was about 79% (Table 2, seventh O.8% W on 196
Ptalumina
27% 3% 190 296 196
row). The molar yield was about 1% for dodecanol, about 2% 2% W on 196 28% 4% 190 296 196
for lauryl laurate, and about 3% for undecane. Ptalumina
0118. These results further demonstrate that a hydrode O.4% W on 2% 27% 79% 2% 196 O%
oxygenation process employing a W/Pt/alumina catalyst Ptalumina
under conditions of low temperature and pressure can be used O.8% W on 29
Ptalumina
30% 11% 3% 296 196
to produce a linear alkane from the Coxygenate, lauric acid. 2% W on 296 42% 24% 10% 3% 196
The hydrodeoxygenation process mostly yielded the com Ptalumina
pletely deoxygenated, full-length product, dodecane, with a 2% W on 5% 99% 80% 79% 3% 3%
very small amount of by-products. The low level of undecane Ptalumina
produced indicates that there was little carbon loss during the 2% Pt on 290 W
on alumina
56% 59 3% 6% 3%
process, while the low levels of dodecanol and lauryl laurate 2% Pt. On 5% W SO% 13% 6% 9% 59
indicate that the carboxylic acid moiety of the lauric acid was on alumina
efficiently deoxygenated. 2% W on 296 Pt 36% 59 2% 6% 296
on alumina
Example 4 5% W on 296 Pt 56% 20% 11% 9% 59
on alumina
2% W and 2% Pt 39% 8% 3% 3% 196
Selective Hydrodeoxygenation of Lauric Acid to on alumina
Dodecane in a 20-cc Multi-Reactor System Using 5% W and 2% Pt 44% 9% 4% 3% 196
Various Catalysts on alumina
5% W on 196 779, 18% 13% 296 196
0119 This Example describes the selective hydrodeoxy Ptalumina
7.5% W on 196 75% 15% 11% 296 196
genation of lauric acid to dodecane using various other cata Ptalumina
lysts aside from the 2% W on 5% Pt/alumina described above. O% W on 196 59% 12% 79% 296 196
For those other catalysts containing platinum and tungsten, Ptalumina
they differed from each other in the amount of platinum and 5% W on 296 93% 61% 57% 3% 3%
tungsten contained therein and/or in the manner in which the Ptalumina
5% W on 296 100% 69% 69% 3% 3%
platinum and tungsten were applied to the alumina Support Ptalumina
during catalyst preparation. Catalysts containing other metals 5% W on 296 99% 56% S6% 296 296
Such as nickel, copper, bismuth, molybdenum, palladium, Ptalumina
manganese, chromium and Vanadium were also tested. 7.5% W on 29 98% 39% 38% 296 296
0120. Other catalysts were prepared and tested for their Ptalumina
O% W on 296 93% 30% 28% 296 296
ability to catalyze deoxygenation of lauric acid to dodecane Ptalumina
following the 20-cc reaction procedure described in Example 5% W on N 47% 4% 2% 296 196
3. These other catalysts are listed in Table 2 and were prepared O% W on N 36% 6% 2% 3% 196
in a manner similar with the protocol described in Example 1 % Pt on N 57% 3% 2% 59 3%
for preparing 2% W on 5% Pt/alumina. In general, catalysts O.S90 Pton N
5% W on 196 Pt
67%
34%
3%
79%
2%
2%
10%
4%
79%
296
containing tungsten and platinum were prepared by impreg on Ni
nating tungsten onto alumina-Supported platinum ("Pt/alu 5% W on O.S90 44% 59 2% 6% 296
mina') or by impregnating tungsten and platinum onto alu Pt on Ni
mina. Alumina was impregnated with other metals 1% Pt and 0.1% 18% 6% 190 6% 196
(vanadium, palladium, manganese, chromium, molybde Cu on carbon
5% Pt and 5% Bl 13% 59 190 9% 196
num) in the preparation of other catalysts. Both the Pt/alu on carbon
mina (refer to Example 1) and alumina were from Johnson 2%. Mo on 2% 85% 296 2% 296 296
Matthey, Inc. Pod on alumina
2% W on 296 Pd 32% 3% 190 4% 196
TABLE 2 on alumina
2% Cr on 29 P. 32% 296 190 4% 196
Molar Selectivity and Molar Yield of Dodecane and Undecane on alumina
from the Conversion of Lauric Acid Using Various Catalysts 2%. Min on 2% 33% 296 190 3% 196
Pod on alumina
Dodecane 2% W on 29 P. 27% 3% 190 4% 196
on alumina
Lauric Acid Selec- Undecane
Reactions performed with listed catalyst under the conditions described in Example 3.
Catalyst Conversion tivity. Yield Selectivity. Yield Percent moles of lauric acid that converted to products,
Percent moles of lauric acid that converted into dodecane or undecane,
O4% W on 1% 45% 196 O% 196 O%
Ptalumina I0121. The catalysts listed in Table 2 as “0.4% W on 1%
Pt/alumina”, “0.8% W on 1% Pt/alumina”, “2% W on 1%
US 2014/0081065 A1 Mar. 20, 2014

Pt/alumina”, “0.4% W on 2% Pt/alumina”, “0.8% W on 2% using three separate preparations of a 5% W on 2% Pt/alu

Pt/alumina”, “2% W on 2% Pt/alumina”, “5% W on 1% mina catalyst had dodecane yields of at least 56%, with unde
Pt/alumina”, “7.5% W on 1% Pt/alumina”, “10% W on 1% cane yields of 3% or lower.
Pt/alumina”, “5% W on 2% Pt/alumina, “7.5% W on 2%
Pt/alumina” and “10% W on 2% Pt/alumina” were prepared Example 5
following the procedures described in Example 1. However,
different concentrations of ammonium tungstate pentahy Selective Hydrodeoxygenation of Lauric Acid to
drate were used accordingly to load tungsten onto Pt/alumina Dodecane in a 20-cc Multi-Reactor System Using
containing either 1% or 2% by weight platinum. Catalysts Containing Alumina of Various pH Levels
0122) The catalysts listed in Table 2 as “2% Pton2% W on 0.125. This Example describes the selective hydrodeoxy
alumina”, “2% Pt on 5% W on alumina”, “2% W on 2% Pton
genation of lauric acid to dodecane using catalysts containing
5% W and 2% Pt supported on an acidic, weakly acidic,
alumina', and “5% Won2% Pton alumina” were prepared by neutral, or basic alumina Solid Support.
sequentially impregnating platinum and tungsten onto alu 0.126 The catalysts in this example were prepared using a
mina. The catalysts 2% Pt on 2% W on alumina and 2% Pton particular type of alumina (acid, weakly acidic, neutral, or
5% W on alumina were prepared by first loading tungsten basic) following the methodology described in Example 4 for
onto alumina (forming alumina-Supported tungsten) fol catalysts designated as “5% W on 2% Pt on alumina’. These
lowed by loading platinum onto the alumina-Supported tung catalysts were then used in a lauric acid hydrodeoxygenation
sten. Oppositely, catalysts 2% Won2% Pton alumina and 5% reaction under the conditions described in Example 3. The
W on 2% Pt on alumina were prepared by first loading plati results of these reactions are listed in Table 3.
num onto alumina (forming alumina-Supported platinum)
followed by loading tungsten onto the alumina-Supported TABLE 3
platinum. Each metal was loaded onto Support in a manner
similar to the process described in Example 1. Briefly, a salt of Molar Selectivity and Molar Yield of Dodecane and
Undecane from the Conversion of Lauric Acid Using
tungsten (ammonium tungstate pentahydrate) or platinum Catalysts Containing Alumina of Various pH
(tetraamine platinum nitrate) was dissolved in deionized
water and then mixed with alumina. The mixture was dried Lauric Acid Dodecane Undecane
for about 16 hours at 110°C. under a vacuum of 20 mm Hg, Catalyst Conversion Selectivity. Yield Selectivity. Yield
cooled, and then calcined for 3 hours at 350° C., yielding
eitheralumina-Supported tungsten or platinum. Impregnation 5% W on 296 53% 41% 22% 4% 296
Pton basic
of the next metal (either tungsten or platinum) was then alumina
performed via this same procedure, but using the alumina 5% W on 296 63% 45% 28% 4% 296
Supported tungstenor platinum produced from the first step as Pton neutral
the loading target. The production of these particular catalysts alumina
5% W on 296 66% 48% 32% 4% 3%
thus involved two calcining steps. Using appropriate metal Pton weakly
salts, similar processes were used accordingly to prepare the acidic
catalysts listed in Table 2 as “2% Mo on 2% Pd on alumina’, alumina
“2% W on 2% Pd on alumina”, “2% Cr on 2% Pd on alu 5% W on 296
Pton acidic
64% 48% 30% 3% 296
mina”, “2% Mn on 2% Pd on alumina and “2% V on 2% Pd alumina
on alumina'.
Reactions performed with listed catalyst under the conditions described in Example 3.
(0123. The catalysts listed in Table 2 as “2% W and 2% Pt Percent moles of lauric acid that converted to products,
on alumina” and “5% W and 2% Pt on alumina” were pre Percent moles of lauric acid that converted into dodecane or undecane,
pared using one calcining step, as follows. A tetraamine plati
num nitrate Solution was mixed with alumina and then dried I0127. The results listed in Table 3 indicate that catalysts
for about 16 hours at 110°C. under a vacuum of 20 mm Hg. containing 5% W and 2% Pt supported on acidic, weakly
The dried product was then mixed with an ammonium tung acidic, neutral, or basic alumina were all capable of cata
state pentahydrate solution and then dried as above. The dried lyzing hydrodeoxygenation of lauric acid to dodecane at 200
product, which contained both platinum and tungsten with C. and 400 psig. All the reactions yielded 22%-32% dode
alumina, was then calcined for 3 hours at 350° C. Using cane, while yielding 3% or less of undecane. These results
appropriate metal salts and carbon as a Support, similar pro Suggest that catalysts containing various amounts oftungsten
cesses were used accordingly to prepare the catalysts listed in and platinum Supported on alumina of various pH levels are
Table 2 as “1% Ptand 0.1% Cu. on carbon and “5% Ptand 5% capable of catalyzing Cos oxygenate hydrodeoxygenation.
Bi on carbon'.
Example 6
0124. The results listed in Table 2 indicate that several
catalysts in addition to 2% W on 5% Pt/alumina are capable of Selective Hydrodeoxygenation of Lauric Acid to
catalyzing hydrodeoxygenation of lauric acid to dodecane at Dodecane in a 20-cc Multi-Reactor System Using a
200° C. and 400 psig. For example, the products of reactions Six-Hour Reaction Period
using catalysts 2% W on 2% Pt/alumina (Table 2, sixth row)
and 5% W on 2% Pt on alumina (Table 2, eleventh row) had I0128. This Example describes the selective hydrodeoxy
molar yields of dodecane that were more than two times genation of lauric acid to dodecane using various catalysts
higher than the respective molar yields of undecane. Also, following the reaction procedure described in Example 3,
reactions using several of the catalysts in Table 2 had molar with the exception that the conditions of 200° C. and 400 psig
yields of dodecane greater than 25%. For example, reactions were held for 6 hours instead of 4 hours.
US 2014/0081065 A1 Mar. 20, 2014

0129. The catalysts in this example containing tungsten opposed to using a ~17:1 mixture of tetradecane and hexade
and Pt/alumina (alumina-Supported platinum) were prepared cane as the solvent. The results of these reactions are listed in
following the procedure described in Example 4. A similar Table 5.
procedure was followed to prepare a 5% Mo on 2% Pt/alu
mina catalyst. These catalysts were then used in a lauric acid TABLE 5
hydrodeoxygenation reaction under the conditions described
in Example 3, except that the reaction conditions of 200° C. Molar Selectivity and Molar Yield of Dodecane and Undecane from
the Conversion of Lauric Acid Using Different Reaction Solvents
and 400 psig were held for 6 hours instead of 4 hours. The
results of these reactions are listed in Table 4. Reaction Lauric
Conditions Acid Dodecane Undecane
TABLE 4 Lauric Conver- Selec- Selec
Molar Selectivity and Molar Yield of Dodecane and Undecane Catalyst Acid Solvent sion tivity. Yield tivity. Yield
from the Conversion of Lauric Acid from a 6-Hour Reaction 2% W on 2g Ole 71.9% 15% 11% 296 196
59% Pt
Lauric Acid Dodecane Undecane alumina
2% W on 1g hexa- 81% 28%. 23% 3% 296
Catalyst Conversion Selectivity. Yield Selectivity. Yield 59% Pt decane
alumina
290 W on 296 88% 82% 71.9% 59 4%
2% W on 1g Water 32% 59% 2% 296 196
Ptalumina
59% Pt
5% W on 296 100% 63% 62% 3% 3%
alumina
Ptalumina
7.5% W on 29 99% 40% 40% 296 296
Ptalumina Results shown for each reaction are an average of two reaction runs.
Percent moles of lauric acid that converted to products,
10% W on 290 100% 82% 82% 3% 3% Percent moles of lauric acid that converted into dodecane or undecane.
Ptalumina
5%. Mo on 2% 98% SO% SO% 3% 3%
Ptalumina I0134. The results listed in Table 5 indicate that catalysts
comprising tungsten and platinum perform well in hydrode
Results shown for tungsten-containing catalysts are an average of two reaction runs.
Percent moles of lauric acid that converted to products, oxygenation reactions that utilize organic solvents such as
Percent moles of lauric acid that converted into dodecane or undecane, hexadecane. However, reactions that do not comprise a sol
vent also work: 2% W on 5% Pt/alumina catalyst in the
0130. The results listed in Table 4 indicate that the reaction absence of solvent was able to catalyze a reaction that yielded
conditions described in Example 3, but using a 6-hour period 15% dodecane with only a 1% yield of undecane.
at 200° C. and 400 psig, allow hydrodeoxygenation of lauric 0.135 Based on this example, and Example 3 in which 2%
acid to dodecane with low production of undecane byproduct. Won 5% Pt/alumina catalyst was used in a solvent containing
Specifically, catalysts with 2% platinum and 2%. 5%, 7.5%, tetradecane and hexadecane, it is apparent that these and
or 10% tungsten were capable of yielding 40%-82% dode similar organic solvents can be used in certain of the Cos
cane with 4% or less undecane yield. oxygenate hydrodeoxygenation processes described herein.
0131 Table 4 also indicates that a catalyst comprising 5%
molybdenum and 2% platinum Supported on alumina was Example 8
effective at catalyzing lauric acid hydrodeoxygenation to
dodecane with little production of undecane. This observa Selective Hydrodeoxygenation of Myristic Acid to
tion Suggests that catalysts comprising platinum and molyb
denum are useful for carrying out certain Cos oxygenate Tetradecane in a 20-cc Multi-Reactor System
hydrodeoxygenation processes as described herein. 0.136. This Example describes the selective hydrodeoxy
genation of myristic acid to tetradecane using the alumina
Example 7 Supported tungsten/platinum catalyst prepared in Example 1
(2% W on 5% Pt/alumina). This process was carried out under
Selective Hydrodeoxygenation of Lauric Acid to the conditions described in Example 3. The results of this
Dodecane in a 20-cc Multi-Reactor System Using reaction, which was done in duplicate, are listed in Table 6.
Various Solvent Conditions
TABLE 6
0132) This Example describes the selective hydrodeoxy
genation of lauric acid to dodecane using catalysts containing Molar Selectivity and Molar Yield of Tetradecane from the
tungsten and platinum following the reaction procedure Conversion of Myristic Acid Using Pt/WAlumina Catalysts
described in Example 3, with the exception that different Myristic
solvents and different amounts of lauric acid substrate were Acid Tetradecane
used.
Catalyst Conversion Selectivity Yield
0133. The catalyst used in this example which contained
2% tungsten and 5% platinum was prepared following the 290 W on 5% Pt 57.51% 52.41% 30.14%
procedures described in Examples 1 and 4. This catalyst was on alumina
then used in a lauric acid hydrodeoxygenation reaction under 290 W on 5% Pt 49.28% 53.05% 26.14%
on alumina
the conditions described in Example 3, with the following
exceptions. The reactions used 1 or 2 grams of lauric acid Percent moles of myristic acid that converted to products,
substrate instead of 0.20 grams lauric acid. Also, either hexa Percent moles of myristic acid that converted into tetradecane,
decane (1 g) alone, water (1 g), or no solvent was used, as
US 2014/0081065 A1 Mar. 20, 2014

0.137 The results in Table 6 demonstrate that a hydrode 250° C. and a hydrogen gas pressure of at least about 300
oxygenation process employing a W/Pt/alumina catalyst psig, wherein the Colis oxygenate is hydrodeoxygen
under conditions of low temperature and pressure can be used ated to a linear alkane, and wherein the linear alkane has
to produce a linear alkane from the C oxygenate, myristic the same carbon chain length as the Cos oxygenate;
acid. Thus, the disclosed process can be used to hydrodeoxy and
genate oxygenates of various carbon chain lengths. b) optionally, recovering the linear alkane produced in step
(a).
Example 9 2. The hydrodeoxygenation process of claim 1, wherein
said Cos oxygenate is a fatty acid or a triglyceride.
Selective Hydrodeoxygenation of Palmitic Acid to 3. The hydrodeoxygenation process of claim 1, wherein
Hexadecane in a 20-cc Multi-Reactor System said feedstock comprises a plant oil or a fatty acid distillate
0.138. This Example describes the selective hydrodeoxy thereof.
genation of palmitic acid to hexadecane using the alumina 4. The hydrodeoxygenation process of claim 3, wherein
Supported tungsten/platinum catalyst prepared in Example 1 said feedstock comprises
(2% W on 5% Pt/alumina). This process was carried out under (i) a plant oil selected from the group consisting of soybean
the conditions described in Example 3. The results of this oil, palm oil and palm kernel oil; or
reaction, which was done in duplicate, are listed in Table 7. (ii) a palm fatty acid distillate.
5. The hydrodeoxygenation process of claim 1, wherein
TABLE 7 said Co.1s oxygenate is palmitic acid, myristic acid, or lauric
acid.
Molar Selectivity and Molar Yield of Hexadecane from the 6. The hydrodeoxygenation process of claim 1, wherein
Conversion of Palmitic Acid Using Pt/WAlumina Catalysts said catalyst comprises about 1% to about 6% by weight of
Palmitic platinum as the first metal and 1.5% to about 15% by weight
Acid Hexadecane oftungsten as the second metal.
7. The hydrodeoxygenation process of claim 6, wherein
Catalyst Conversion Selectivity Yield said catalyst comprises about 4% to about 6% by weight of
290 W on 596 Pt 74.05% 57.84% 42.83% platinum as the first metal and about 1.5% to about 2.5% by
on alumina weight of tungsten as the second metal.
290 W on 596 Pt
on alumina
58.54% 71.28% 41.73% 8. The hydrodeoxygenation process of claim 7, wherein
said catalyst comprises about 5% by weight of platinum as the
Percent moles of palmitic acid that converted to products. first metal and about 2% by weight of tungsten as the second
Percent moles of palmitic acid that converted into hexadecane, metal.
9. The hydrodeoxygenation process of claim 6, wherein
0.139. The results in Table 7 demonstrate that a hydrode said catalyst comprises about 2% by weight of platinum as the
oxygenation process employing a W/Pt/alumina catalyst first metal and about 5% to about 10% by weight oftungsten
under conditions of low temperature and pressure can be used as the second metal.
to produce a linear alkane from the C oxygenate, palmitic 10. The hydrodeoxygenation process of claim 1, wherein
acid. This example further demonstrates that the disclosed said catalyst further comprises a solid Support.
process can be used to hydrodeoxygenate oxygenates of vari 11. The hydrodeoxygenation process of claim 10, wherein
ous carbon chain lengths. said Solid Support comprises Al2O.
What is claimed is:
1. A hydrodeoxygenation process for producing a linear 12. The hydrodeoxygenation process of claim 1, wherein
alkane from a feedstock comprising a saturated or unsatur said temperature is about 200° C. and said pressure is about
ated Cos oxygenate comprising a moiety selected from the 400 psig.
group consisting of an ester group, carboxylic acid group, 13. The hydrodeoxygenation process of claim 1, wherein
carbonyl group, and alcohol group, wherein the process com the feedstock and the catalyst are contacted in an organic
solvent.
prises:
a) contacting said feedstock with a catalyst comprising (i) 14. The hydrodeoxygenation process of claim 13, wherein
about 0.1% to about 10% by weight of a first metal the organic solvent comprises tetradecane, hexadecane, or a
mixture thereof.
selected from Group IB or VIII of the Periodic Table, and 15. The hydrodeoxygenation process of claim 1, wherein
(ii) about 0.5% to about 15% by weight of a second the molar yield is less than 10% for a reaction product having
metal selected from the group consisting of tungsten,
rhenium, molybdenum, Vanadium, manganese, Zinc, a carbon chain length that is one or more carbonatoms shorter
chromium, germanium, tin, titanium, gold and Zirco than the carbon chain length of the Cos oxygenate.
nium, at a temperature between about 150° C. to about k k k k k