US008O84655B2

(12) United States Patent (10) Patent No.: US 8,084,655 B2

Dindi et al. (45) Date of Patent: *Dec. 27, 2011

(54) CATALYTIC PROCESS FOR CONVERTING 2006/0207166 A1 9, 2006 Herskowitz et al.

RENEWABLE RESOURCES INTO 2006/0252950 A1 11/2006 Ginosar et al.
2006/0260186 A1 11/2006 Iversen et al.
PARAFFINS FOR USE AS DESEL, BLENDING 2006/0264684 A1 11/2006 Petri et al.
STOCKS 2006/0293533 A1 12/2006 Iyer
2007/0010682 A1* 1/2007 Myllyoja et al. .............. 554,174
2007/0066838 A1 3/2007 Hillion et al.
(75) Inventors: Hasan Dindi, Wilmington, DE (US); 2007/0068848 A1 3/2007 Monnier et al. ................ 208/15
Sourav K. Sengupta, Wilmington, DE 2007/0073070 A1 3/2007 Hillion et al.
(US); Andrew Francis Gonzon, 2007/008305.6 A1 4/2007 Srinivas et al.
Newark, DE (US); David Richard 2007/O135669 A1 6/2007 Koivusalmi et al.
2007/0170091 A1 7/2007 Monnier et al.
Corbin, West Chester, PA (US) 2007/O175795 A1 8, 2007 Yao et al.
2007/0225.383 A1 9/2007 Cortright et al.
(73) Assignee: E. I. du Pont de Nemours and 2007/0260102 A1* 1 1/2007 Duarte Santiago et al. .. 585/733
Company, Wilmington, DE (US) 2008/0269352 A1 10, 2008 Falkowski et al.
2009.0062578 A1 3/2009 Koivusalmi et al. ............ 585/14
*) Notice: Subject to anyy disclaimer, the term of this FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35
U.S.C. 154(b) by 242 days. BR 2004 004310 5, 2006
BR 2005 OO3215 12/2006
This patent is Subject to a terminal dis BR 2005 OO2795 2, 2007
claimer. EP 1724, 325 11, 2006
EP 1741 767 A1 1, 2007
EP 1741 768 A1 1, 2007
(21) Appl. No.: 12/138,764 ES 224.5270 12/2005
FR 2890961 3, 2007
(22) Filed: Jun. 13, 2008 JP 200605.0954 2, 2006
JP 2006104316 4/2006
(65) Prior Publication Data JP 2006213829 8, 2006
MX 2004.005349 12/2005
US 2008/O3O8458A1 Dec. 18, 2008 SU 1162479 6, 1985
WO WO 98.30323 7, 1998
Related U.S. Application Data WO WO99/09 116 2, 1999
WO WO 2004/048311 A1 6, 2004
(60) Provisional application No. 60/934,710, filed on Jun. WO WO 2006/084.048 A1 8, 2006
15, 2007. WO WO 2006/11 1997 A1 10/2006
WO WO 2006/119357 A3 11/2006
WO WO2007OO3708 * 1 2007
(51) Int. Cl. WO WO 2007/020465 A1 2, 2007
CD7C I/00 (2006.01) WO WO 2008/020048 A2 2, 2008
(52) U.S. Cl. ......................... 585/240; 585/242:585/733 OTHER PUBLICATIONS
(58) Field of Classification Search .................. 585/240,
585/242, 733 Furimsky, Mechanism of Catalytic Hydrodeoxygenation of
See application file for complete search history. Tetrahydrofuran; Industrial & Engineering Chemistry Product
Research and Development (1983), 22(1), 31-34; Publisher: The
(56) References Cited American Chemical Society Abstract.
Levy et al., Alkane liquid fuels production from biomass, Liq. Fuel
U.S. PATENT DOCUMENTS Dev. (1983), 159-88; Pub: CRC, Boca Raton, Florida, USA. Abstract.
4472,266 A * 9/1984 Oleck et al. .............. 208/111.15 (Continued)
4,554.397 A 11, 1985 Stern et al.
4,655,906 A 4, 1987 Bjornson et al. Primary Examiner — Nina Bhat
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4,992,605 A * 2/1991 Craig et al. ................... 585,240 (57) ABSTRACT
5,705,722 A * 1/1998 Monnier et al. .............. 585,240
6,005,143 A 12/1999 Machado et al. A process for converting renewable resources such as Veg
7,169,291 B1 1/2007 Wang etable oil and animal fat into paraffins in a single step which
7,232,935 B2 * 6/2007 Jakkula et al. ................ 585,240
7.459,597 B2 * 12/2008 Koivusalmi et al. 585,733 comprises contacting a feed which is a renewable resources
7.550,634 B2* 6/2009 Yao et al. ............ 585,240 with hydrogen and a catalyst which comprises a non-precious
7,626,063 B2 * 12/2009 Ghomasgi et al. 585,276 metal a first oxide and optionally a second oxide wherein at
2004/0230085 A1* 11/2004 Jakkula et al. ................ 585,240 least one of the first oxide or second oxide comprises a Zeolite,
2005/OO39383 A1 2, 2005 Wu
2005, 0120621 A1 6/2005 Lawson et al. through hydrodeoxygenation and one or both of hydroi
2005/0274.065 A1 12, 2005 Portnoff et al. Somerization and hydrocracking.
2006, 0080891 A1 4/2006 Ghosh et al.
2006, O161032 A1 7/2006 Murzin et al. 20 Claims, No Drawings
 US 8,084,655 B2
Page 2

OTHER PUBLICATIONS Twaiq et al., Catalytic conversion of palm oil over mesoporous
aluminosilicate MCM-41 for the production of liquid hydrocarbon
Elliott et al., Hydrodeoxygenation of wood-derived liquids to pro fuels; Fuel processing Technology (2003), 84, 105-120; Elsevier
duce hydrocarbon fuels; Proceedings of the InterSociety Energy Con Science B.V.
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Pacific Northwest Lab., Richland, Washington, USA. Abstract. cracking over aluminosilicate mesoporous catalysts with various
Held et al., Production of hydrocarbons from biomass; Comm. Eur, Si/Al rations; Microporous and Mesoporous Materials (2003), 64.
Communities, Rep. EUR (1985), EUR 10024. Energy Biomass, 95-107; Elsevier, Inc.
744-8; Germany. Abstract. Chiranjeevi et al. Effect of Si/Al ratio of HMS Support on catalytic
Ooi et al., Reaction of palm Stearin catalyzed by nickel (II) ion functionalities of Mo, CoMo, NiMo hydrotreating catalysts; Cataly
exchanged Zeolite 13X. Formation of hydrocarbons; Yukagaku sis Communications (2005), 6(2), 101-106; Publisher: Elsevier B.V.
(1986), 35(5), 354-8; Palm Oil Res. Inst., Kuala Lumpur, Malaysia. Criterion DN-2318 Catalyst, Material Safety Data Sheet dated Feb.
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Ratcliff et al., Hydrodeoxygenation of lignins and model com 23, 2005; Criterion Catalysts & Technologies L.P., Houston, Texas,
pounds; Applied Biochemistry and Biotechnology (1988), 17, 151 USA.
160; Chem. Convers. Res. Branch, Solar Energy Res. Inst., Golden, Criterion DN-3330 Catalyst, Material Safety Data Sheet dated Feb.
Colorado 80401, USA. Abstract. 23, 2005; Criterion Catalysts & Technologies L.P., Houston, Texas,
Ratcliff et al., Hydrodeoxygenation of a lignin model compound; USA.
Res. Thermochem. Biomass Convers. Ed. Rev. Pap. Int. Conf. Liu et al., Hydrotreating reaction performance over CoMo-Catalyzed
(1988); Publisher: Elsevier, London, UK. Abstract. fx-alumina monolith catalyst; Abstracts of Papers, 230' ACS
Gellerman et al., Study of spent hydrorefining catalysts; Khimiya i National Meeting, Washington, DC, USA, Aug. 28-Sep. 1, 2005,
Tekhnologiya Topliv i Masel (1993), (8), 32-34; VNII NP, Russia. PETR-048; Publisher: American Chemical Society, USA. Abstract.
Abstract. Machado et al., Applying monolith reactors for hydrogenations in the
Stumborg et al., Catalytic conversion of vegetable oils to diesel production of specialty chemicals process and economic consider
additives; Energy from Biomass and Wastes. (1993), 16, 721-38; ation; Catalysis Today (2005) 105, 305-317; Elsevier.
Canada. Abstract. Senol et al. Hydrodeoxygenation of aliphatic esters on Sulphided
Laurent et al. Hydrodeoxygenation of oxygenated model com NoMofy-Al-O and CoMofy-AlO3 catalyst: The effect of water;
pounds: Simulation of the hydropurification of bio-oils; Adv. Catalysis Today (2005), 106(1-4), 186-189; Publisher: Elsevier B.V.
Thermochem. Biomass Convers. Ed. Rev. Pap. Int, conf. 3 Wang et al. Studies on nickel-based bimetallic catalysts for
(1994); Publisher: Blackie, Glasgow, UK. Abstract. hydrodeoxygenation; Ranliao Huaxue Xuebao (2005), 33(5), 612
Wong et al., Conversion of vegetable oils and animal fats into paraf 616; Publisher: KeXue Chubanshe, China. Abstract.
finic cetane enhancers for diesel fuels; Proceedings, Biomass Con Yang et al., Effect of Mo, Waddition on performance of Ni/Al2O3
ference of the Americas: Energy, Environment, Agriculture and catalysts for hydrodeoxygenation; Huagong Jinzhan (2005), 24(12),
Industry. 2", Portland, Oregon, USA, Aug. 21-24, 1995, 902-910; 1386-1389; Publisher Huaxue Gongye Chubanshe, China. Abstract.
Publisher: National Renewable Energy Laboratory, Golden, Colo
rado, USA. Abstract. Petrus et al., Biomass to biofuels, a chemical perspective; Green
Bridgewater, Production of high grade fuels and chemicals from Chemistry (2006), 8(10), 861-867; Royal Society of Chemistry,
catalytic pyrolysis of biomass; Catalysis Today (1966), 29, 285-295; Amsterdam, The Netherlands. Abstract.
Elsevier Science B.V. Snåre et al., Heterogeneous Catalytic Deoxygenation of Stearic Acid
Horne et al., Premium grade hydrocarbons from the catalytic treat for Production of Biodiesel; Ind. Eng. Chem. Res. (2006), 45,5708
ment of pyrolysis vapors derived from biomass; Biomass for Energy 5715; American Chemical Society.
and the Environment, Proceedings of the European Bioenergy Con Stadlbauer et al., Production of hydrocarbons from animal fat by
ference, 9', Copenhapen, Jun. 24-27, 1996, vol. 3, 1601-1606; Pub thermocatalytic cracking; Erdoel. Erdgas, Kohle (2006), 122(2), 64.
lisher: Elsevier, Oxford, UK. Abstract. 66-69; Publisher: Urban-Verlag Hamburg/Wien GmbH, Germany.
Okuda et al., Hydrodeoxygenation of phenol derivatives using Abstract.
Ni-Mo/Al2O3 and Co-Mo/Al2O3 catalysts; Sekiuy Gakkaishi Busnardo et al., Processing of spent NiMo and CoMo/Al2O3 cata
(1997), 40(3), 192-198; Dep. Chem. Eng., Fac. Eng., Kansai Univ., lysts via fusion with KHSO4; Journal of Hazardous Materials (2007),
Suita, Osaka, 564, Japan. Abstract. 139(2), 391-398; Publisher: Elsevier B.V.
Leng et al., Catalytic conversion of palm oil to fuels and chemicals; Demirbas, Production of gasoline and diesel fuels from bio-materi
Canadian Journal of Chemical Engineering (1999), 77(1), 156-162; als; Energy Sources, part A: Recovery, Utilization, and Environmen
Canadian Society for Chemical Engineering. Abstract. tal Effects (2007), 29(8), 753-760; Taylor & Francis, Inc. Abstract.
Song et al., Mesoporous molecular sieve MCM-41 supported Co-Mo Huber et al., Processing biomass in conventional oil refineries: Pro
catalyst for hydrodesulfurization of dibenzothiophene in distillate duction of high quality diesel by hydrotreating vegetable oils in heavy
fuels; Applied Catalysis A: General (1999), 176(1), 1-10; Publisher: vacuum oil mixtures; Applied Catalysis, A: General (2007), 329,
Elsevier Science B.V. 120-129; Elsevier B.V.
Twaiq et al., Catalytic Conversion of Palm Oil to Hydrocarbons: Delmon, Catalysts in petroleum refining 1989; Studies in Surface
Performance of Various Zeolite Catalysts; Ind. Eng. Chem. Res. Science and Catalysis; (1990), 1-38; Publisher: Elsevier B.V.
(1999), 38, 3230-3237; American Chemical Society. Dwyer, Zeolite structure, composition and catalysis; Chemistry and
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Publisher: Zhongguo Shihua Chubanshe, China. Abstract. * cited by examiner
 US 8,084,655 B2
1. 2
CATALYTIC PROCESS FOR CONVERTING (e.g., lithium, sodium and potassium) and/or fluorine, boron,
RENEWABLE RESOURCES INTO and phosphorus. The catalyst is activated by simultaneous
PARAFFINS FOR USE AS DESEL, BLENDING reduction and Sulfidation in place before subjecting it to
STOCKS hydrotreating reactions. Catalysts consisting of molybdenum
Supported on alpha-alumina with promoters such as cobalt
FIELD OF THE INVENTION (Co-Mo? Al-O.) or nickel (Ni Mo/Al2O) are extensively
used in the hydrotreating of petroleum fractions and resids.
The present invention relates to a process and a catalyst for The catalyst most commonly used for the production of
the production of linear and branched paraffins (hydrocar diesel from renewable resources comprises a precious metal
bons) from renewable resources that are useful as a blending 10 Such as platinum and/or palladium. Murzin et al. in Industrial
stock for diesel fuel for use in warm and cold climates. Engineering Chemical Research, Vol. 45 (2006) pp. 5708
5715, disclose numerous metals used for such catalysis. Plati
BACKGROUND OF THE INVENTION num and palladium gave the best conversion of desired prod
ucts. Nickel catalysts produced unwanted heavier products
The high cost and increased environmental footprint of 15 Such as dimers due to the recombination of moieties resulting
fossil fuels and limited petroleum reserves in the world have from extensive cracking of the feed material.
increased the interest in renewable fuel sources. Renewable Processes are known to produce green diesel. Such pro
resources include ethanol from corn and Sugar for use in cesses Suffer from one or more deficiencies such as requiring
automobiles, and plant oils for use as diesel fuel. Research in multiple steps, multiple reactors, different catalysts per step
the diesel fuel area includes two main areas, bio-diesel and and expensive precious metal catalysts.
green diesel. While there have been great efforts in the green diesel
Transesterification of fatty acids in triglycerides into research area, there remains a need for a process of
methyl esters using methanol and a catalyst Such as sodium hydrotreating of a renewable feed source where the hydrode
methylate produces FAME (Fatty Acid Methyl Ester), which oxygenation, hydroisomerization and hydrocracking pro
is commonly referred to as bio-diesel. These methyl esters, 25 cesses are simplified using a less expensive, non-precious
mainly linear C to C carboxylic acids, can be used as fuel metal catalyst.
or can be blended into diesel refined from crude oil sources.
The transesterification reaction is complex. To be used as SUMMARY OF THE INVENTION
diesel fuel, costly modification of diesel engine is necessary
as well as conversion of associated piping and injector con 30 Provided is a process for hydrotreating which comprises
figurations. Other disadvantages include poor performance of (a) providing a feed which is a renewable resource; (b) con
bio-diesel in cold weather applications, limiting its world tacting the feed with a catalyst in the presence of hydrogen at
wide use to warmer climates, and poor emissions. In addition, a temperature of 250 to 425° C. and a pressure of 500 to 2500
use of bio-diesel increases maintenance costs due to poor psig (3,450 to 17.250 kPa), to produce a paraffin (hydrocar
lubricity, increased viscosity, and high oxygen content. Bio 35 bon) product, wherein the catalyst comprises one or more
diesel, while a renewable resource, brings a high cost of use active metals and a first oxide and optionally a second oxide
for processing and use in engines. wherein at least one of the first oxide or the second oxide
Diesel from renewable resources, commonly referred to as comprises a Zeolite. In this process, hydrodeoxygenation and
green diesel, involves converting the fatty acids in triglycer one or both hydrocracking and hydroisomerization may
ides into linear alkanes via hydrodeoxygenation (HDO). The 40 occur in a single step.
triglyceride backbone is converted to propane and separated. The active metals used in the process of this invention are
Green diesel can be used as a fuel by itself or as a mixture with non-precious metals including nickel, cobalt, molybdenum,
diesel from petroleum feedstocks (petro diesel) with little to tungsten and combinations of two or more thereof. For long
no engine modification and can be processed in refineries term performance and activity, the catalyst may be initially
currently refining crude oils. Current processes involve mul 45 sulfided in situ or ex situ and the feed may be supplemented
tiple steps to obtain green diesel fuel with comparable prop periodically by a Sulfiding agent (Sulfur containing com
erties with petro diesel. Steps include hydrodeoxygenation, pound). Sulfiding is particularly advantageous when the cata
hydroisomerization and/or hydrocracking. lyst comprises molybdenum.
Delmon, B. “Catalysts in Petroleum Refining 1989” in: The first oxide comprises a mono- or mixed metal oxide, a
Studies in Surface Science and Catalysis, Eds. Trimm, D. L., 50 Zeolite, or a combination of two or more thereof. The first
Akashah, S., Absi-Halabi, M., and Bishara, A. (Elsevier, oxide is used as a support for the active metal. The first oxide
Amsterdam, 1990), pp 1-38, discloses the transformation of a can be alumina, silica, titania, Zirconia, kieselguhr, silica
very large portion of crude oil to usable products depends on alumina or combinations of two or more thereof. Silica-alu
cracking and hydrotreating processes. Over the last several mina includes zeolites. Preferably the first oxide is alumina,
decades, hydrotreating processes have become more complex 55 silica or a combination thereof.
and diversified and includes Such processes as, hydropurifi When the first oxide is not a zeolite, the catalyst comprises
cation (e.g., removal of Sulfur, nitrogen, oxygen, metals, etc.), a second oxide, which comprises a Zeolite. The second oxide
hydroconversion (e.g., production of jet fuels or lubricants), can be physically bonded to or mixed with the metal Sup
and hydrocracking (mild or heavy hydrocracking). Specifi ported on the first oxide.
cally, the removal of Sulfur, nitrogen, oxygen, and metals are 60
called hydrodesulfurization, hydrodenitrogenation, hydrode DETAILED DESCRIPTION OF THE INVENTION
oxygenation, and hydrodemetallization, respectively.
Certain hydrotreating catalysts for use with petroleum All tradenames used herein are shown in capital letters.
feedstocks comprise one or more non-precious metals such as The present invention relates to the production of diesel
nickel, cobalt, molybdenum and tungsten supported on 65 fuel from renewable resources wherein hydrodeoxygenation
mono- or mixed-metal oxides such as alumina, silica or silica and one or both hydroisomerization and hydrocracking may
alumina. The catalysts can be promoted by Group I metals occur in a single step under hydrotreating conditions over a
 US 8,084,655 B2
3 4
catalyst comprising a non-precious metal and a first oxide, ditions and feed compositions. A detailed Sulfiding procedure
wherein the first oxide is a Support, and optionally a second is described below in the Examples.
oxide. The process produces substantially linear Saturated Optionally, a metal promoter may be used with the active
hydrocarbons with mild branched and mild cracked moieties. metal in the process of the present invention. Suitable metal
These hydrocarbons can be used as diesel fuel or as an addi promoters include: 1) those elements from Groups 1 and 2 of
tive to blend with petro diesel and possess similar character the periodic table; 2) tin, copper, gold, silver, and combina
istics and performance of petro diesel. Examples of appropri tions thereof; and 3) combinations of group 8 metals of the
ate feed include but are not limited to vegetable oils, animal periodic table in lesser amounts.
oils, and oils from wood. The active metal, including whether reduced or sulfided,
Renewable Resources 10 will be selected based on the desired product.
The feed is a liquid feed, which is a renewable resource and The first oxide comprises a mono- or mixed metal oxide,
can be any plant or animal derived oils, fats, free fatty acids Zeolite, and combinations thereof used as a Support for the
and the like. The renewable resources can be any oil, e.g., active metal. The first oxide is used as a support for the active
Such as those containing triglycerides or free fatty acids, metal. Materials frequently used as the first oxide are porous
where the major component comprises aliphatic hydrocarbon
15 Solids with high total Surface areas (external and internal)
which can provide high concentrations of active sites per unit
chains having C to Co. moieties. Preferably the feed is an oil weight of catalyst. The first oxide may enhance the function
derived from plants and/or animals, comprising one or more of the active metal; and Supported catalysts are generally
triglycerides. The feed may comprise a mixture of triglycer preferred because the metal is used more efficiently.
ides. These triglycerides can be derived from a plant selected The first oxide comprises a porous solid oxide with high
from the group consisting of pine, rape seed, Sunflower, jath total Surface areas (external and internal) which can provide
ropa, seashore mallow and combinations of two or more high concentrations of active sites per unit weight of catalyst.
thereof. The feed can also be a vegetable oil selected from the Preferably the first oxide has pores of a relatively small diam
group consisting of canola oil, palm oil, coconut oil, palm eter, that is preferably 50 nm or less. Preferred first oxides
kernel oil, Sunflower oil, soybean oil, crude tall oil, and com 25 have a surface area greater than 20 m/g, more preferably, the
binations of two or more thereof. The feed source may also first oxide has a surface area greater than 75 m/g, still more
comprise poultry fat, yellow grease, tallow, used vegetable preferably the first oxide has a surface area of at least 100
oils, or oils from pyrolysis of biomass. The feed may also be m?g. Generally surface area is less than 300 m/g.
oils derived from marine life, such as algae. The process is The first oxide can be any porous solid oxide with high
very flexible and selection of the feed is based on availability 30 Surface area including, but not limited to, oxides such as
and cost. silica, alumina, titania, titania-alumina, titania-silica, calcium
Catalyst oxide, barium oxide, zirconia, lanthanum oxide, magnesium
The catalyst comprises an active metal, a first oxide and oxide, kieselguhr, silica-alumina, including Zeolites, and Zinc
optionally a second oxide. The active metal is one or more oxide. The first oxide is preferably selected from the group
non-precious metals. The first oxide comprises a mono- or 35 consisting of alumina, silica, titania, Zirconia, kieselguhr,
mixed metal oxide, Zeolite, or combinations of two or more silica-alumina and combinations thereof. More preferably the
thereof, and is used as a Support. When a second oxide is used first oxide is alumina, silica, kieselguhr, or a combination
it comprises a Zeolite. thereof.
In one embodiment of this invention, the catalyst com The catalyst may further comprise other materials includ
prises an active metal and a first oxide, which may or may not 40 ing carbon, Such as activated charcoal, graphite, and fibril
be a Zeolite. The catalyst may or may not comprise molybde nanotube carbon, as well as calcium carbonate, calcium sili
l, cate and barium sulfate.
The active metals can be nickel (Ni), cobalt (Co), molyb When the first oxide is not a zeolite, the catalyst may
denum (Mo), tungsten (W), or mixtures thereof, e.g., nickel comprise a second oxide, which comprises a Zeolite. The
molybdenum (NiMo), cobalt-molybdenum (CoMo). Prefer 45 second oxide can be physically bonded to or mixed with the
ably, the active metal is Ni. The metal(s) may be either in the active metal Supported on the first oxide.
reduced or sulfided (e.g., NiSs. CoSs. MoS) form. When The second oxide comprises one or more Zeolites. The
the active metal is nickel, higher amounts, such as at least 40 second oxide is particularly important for hydroisomerization
wt %, are needed to reduce in the presence of alumina as the and hydrocracking in the event the first oxide is not a Zeolite.
first oxide. 50 That is, if the first oxide does not comprise a zeolite, then a
In a reducing step, the catalyst is treated with hydrogen, second oxide, which comprises a Zeolite, is advantageously
preferably at elevated temperatures, such as from 100° C. to used whenhydroisomerization and hydrocracking are desired
400°C. Typically the catalyst temperature is increased during reaction processes. Zeolites can be generically described as
hydrogen flow, such as starting at a temperature of about 130° complex aluminosilicates characterized by a three-dimen
C. and increasing to a temperature of 250° C. or 350° C. Such 55 sional framework structure enclosing cavities occupied by
methods are known to those skilled in the art. A particular ions and water molecules, all of which can move with signifi
procedure for reducing catalyst is provided below in the cant freedom within the Zeolite matrix. In commercially use
Examples. ful zeolites, the water molecules can be removed from or
The catalyst may be sulfided by contacting the prepared replaced within the framework without destroying its struc
catalyst with a Sulfur-containing compound Such as thiols, 60 ture. Zeolites can be represented by the following formula:
sulfides, disulfides, HS, or combinations thereof at elevated M.O.AlOxSiOyHO, wherein M is a cation of valence
temperatures. The catalyst can be sulfided before it is used or n, X is greater than or equal to 2, andy is a number determined
during the hydrotreating process by introducing a small by the porosity and the hydration state of the Zeolite, gener
amount of Sulfur-containing compounds, such as thiols, Sul ally from 0 to 8. In naturally occurring zeolites, M is princi
fides, disulfides, HS, poultry fat, or combinations of two or 65 pally represented by Na, Ca, K, Mg and Ba in proportions
more thereof, in the feed. Sulfiding may be important for the usually reflecting their approximate geochemical abundance.
long term activity of the catalyst, depending on reaction con The cations M are loosely bound to the structure and can
 US 8,084,655 B2
5 6
frequently be completely or partially replaced with other content range is from about 0.2 wt % to about 75 wt %. A
cations or hydrogen by conventional ion exchange. further preferred active metal content range is from about 0.5
The Zeolite structure is a corner-linked tetrahedra with Al wt % to about 60 wt %.
or Si atoms at centers of tetrahedra and oxygen atoms at In one embodiment of this invention, a hydrocarbon is
corners. Such tetrahedra are combined in a well-defined produced having a higher ratio of odd-numbered to even
repeating structure comprising various combinations of 4-, numbered hydrocarbons. In this process, the active metal
6-, 8-,10-, and 12-membered rings. The resulting framework preferably comprises nickel, more preferably, does not com
is one of regular channels and cages, which impart a useful prise molybdenum. The nickel content of the catalyst for this
pore structure for separation. Pore dimensions are determined process is at least 40 wt % (combined nickel and nickel
by the geometry of the aluminosilicate tetrahedral forming 10 oxide). Preferably, the nickel content is 40 wt % to 90 wt %,
the Zeolite channels or cages, with nominal openings of 0.26 more preferably, 45 wt % to 60 wt %.
nm for 6-membered rings, 0.40 nm for 8-membered rings, In one embodiment of this invention, a hydrocarbon is
0.55 nm for 10-membered rings and 0.74 nm for 12-mem produced having a higher ratio of even-numbered to odd
bered rings (these numbers assume ionic radii for oxygen). numbered hydrocarbons. In this process, the active metal
Those skilled in the art will recognize that Zeolites with the 15 preferably comprises nickel, cobalt and molybdenum. The
largest pores being 8-membered rings, 10-membered rings, nickel content of the catalyst for this process is generally
and 12-membered rings are considered Small, medium, and between 0.2 wt % and 20 wt %, more preferably, between 0.5
large pore Zeolites, respectively. Pore dimensions are critical wt % and 15 wt %.
to the performance of these materials in catalytic and separa The Zeolite can be present in any amount. Preferably the
tion applications, since this characteristic determines whether Zeolite is present in an amount of at least 10 wt %, based on
reactant molecules can enter and product molecules (in the the total catalyst weight, to achieve Some hydrocracking and
catalytic application case) can exit the Zeolite framework. In hydroisomerization. Preferably, the Zeolite is present in an
practice, it has been observed that very slight decreases in ring amount of at least 25 wt %, more preferably 25-50 wt %.
dimensions can effectively hinder or block movement of par Hydrotreating Process
ticular reactants or catalysis products within a Zeolite struc 25 The hydrotreating process may comprise, but is not limited
ture. to, three major reactions: hydrodeoxygenation (HDO),
Zeolites are available from various sources. A comprehen hydroisomerization (HI) and/or hydrocracking (HC). It is
sive listing of Zeolites vendors is disclosed in “CEH Market known in the art that minor reactions can occur during these
ing Research Report: Zeolites” by, 2005, Chemical Econom steps without significantly altering the desired product.
ics Handbook-SRI International. 30 The HDO process is the removal of oxygen from the fatty
Acid forms of molecular sieve sorbents can be prepared by acids in triglycerides and other free fatty acids to produce a
a variety of techniques including ammonium exchange fol paraffin (hydrocarbon) product. The HDO can occur either as
lowed by calcination or by direct exchange of alkali ions for a decarbonylation, decarboxylation or hydrodeoxygenation
protons using mineral acids or ion exchangers (for a discus or a combination thereof. Decarboxylation refers to the pro
sion of acid sites in Zeolites see J. Dwyer, "Zeolite, Structure, 35 cess of removal of oxygen as carbon dioxide producing a
Composition and Catalysis” in Chemistry and Industry, Apr. paraffinic hydrocarbon. Decarbonylation refers to the process
2, 1984). of removal of the oxygen as carbon monoxide and water
Preferred Zeolites are selected from those having medium directly creating an unsaturated hydrocarbon or indirectly by
(10-membered ring) and large (12-membered ring) pore adding hydrogen to produce a saturated hydrocarbon. Hydro
groups. More preferably, the Zeolite is selected from the 40 deoxygenation refers to the process of removal of oxygen as
group consisting of MFI (ZSM-5), MEL (ZSM-11), FAU water by adding hydrogen. In decarboxylation and decarbo
(zeolite Y or USY), MOR (mordenite), and BEA (beta). nylation, the resulting paraffinic hydrocarbon is one carbon
Physically mixing the active metal or the active metal and unit shorter than the corresponding carboxylic acid. In hydro
first oxide (supported metal catalyst) with zeolites is suffi deoxygenation, the resulting hydrocarbon has the same num
cient, but one can also co-extrude or pelletize the Supported 45 ber of carbons as the corresponding carboxylic acid.
metal catalyst and Zeolite after intimately mixing the two, if Advantageously, the present invention may be tailored to
one desires to do so. A benefit of physically mixing is that the control the route of oxygen removal. For processes that desire
relative concentrations of metal/first oxide and second oxide, minimal use of hydrogen, the decarboxylation and direct
thus the catalyst composition, can be changed. Varying the decarbonylation routes can be used. For a process that desires
catalyst composition changes the composition of the green 50 minimal evolution of carbon monoxide and carbon dioxide,
diesel product. the indirect decarbonylation or hydrodeoxygenation are the
The catalyst can be prepared using any of a variety of ways preferred routes.
known in the art. Preferably, a preformed (e.g., already cal Controlling the route of oxygen removal also impacts the
cined) first oxide is used. For example, the first oxide is chain length of the paraffins in the treated feed. The chain
preferably calcined before application of the active metal. 55 length may play an important role in determining which par
The method of placing the active metal on the first oxide is not ticular deoxygenation process to use. For renewable
critical. Several methods are known in the art. Many suitable resources having 18-carbon chains, there may be a preference
catalysts are available commercially. for n-heptadecane (product of decarbonylation or decarboxy
Relative proportions of active metal and first and optional lation) or n-octadecane (product of hydrodeoxygenation with
second oxides, while not critical, are important in that if too 60 hydrogen consumption). n-Heptadecane (C7) has a lower
little active metal is present, initial activity will be lower than melting point than n-octadecane (Cs), which in turn affects
desired and a long activation period may be required for the the cold-performance characteristics of the diesel blending
catalyst to reach maximum activity. It will be appreciated that stock. Additionally, producing C, removes oxygen from the
the higher the weight percent of active metal, the faster the fatty acid primarily as CO and/or CO (reduced hydrogen
reaction. A preferred content range of the active metal in the 65 consumption) whereas making Cs hydrocarbons removes
catalyst is from about 0.1 wt % to about 90 percent by weight oxygen primarily in the form of H2O (reduced greenhouse gas
of the total supported catalyst. A more preferred active metal emissions). Depending on the conditions, one may prefer C7
 US 8,084,655 B2
7 8
or Cs hydrocarbons. These routes can be selectively con comprises nickel, cobalt and molybdenum. When the renew
trolled by varying the type and/or composition of the catalyst able resource comprises over 50% Cs-based components,
as described herein. Such as triglycerides, the process generally favors hydrode
Straight chain hydrocarbons, specifically in C, to Cs oxygenation rather than decarbonylation and/or decarboxy
chain lengths, provide good cetane numbers but possess poor 5 lation.
cold weather capabilities. Hydroisomerization and hydroc Surprisingly, use of non-precious metals such as nickel,
racking improve the cold weather properties. In hydroisomer cobalt, molybdenum, or combinations thereof in the
ization, a straight chain hydrocarbon is converted into a hydrotreating process of this invention produces yields of
branched hydrocarbon. Preferably, isomerization is con hydrotreated product equivalent or better yields produced
trolled so that the branched hydrocarbon or the mixture of 10
using the more expensive, precious metal catalysts such as
linear and branched hydrocarbons boils in the range of petro disclosed in U.S. Patent Publication 2006/0207166. Yields of
diesel. Hydrocracking reduces the chain length. Shorter
hydrocarbons provide a lower melting component in green 90% or better by volume can be achieved with the desired
diesel or as an additive to petro diesel. HI and HC both ratio of C, to Cs of between 0.05 to 0.95 (based on the desire
Substantially improve the cold weather properties of green 15 to reject oxygen either as CO or HO)and the desired ratio of
diesel by lowering the cloud and pour points. branched (isomerized) to the normal (straight) hydrocarbon
Combining process steps, as in one alternative described can be varied from 0.05 to 0.95% based on the desire for low
herein, is advantageous for numerous reasons. Successfully pour point (more branched) or the desire for increased cetane
combining the steps decreases the need for additional invest number (more Straight chain).
ment. A single reactor is used in the present invention to The present invention may be performed in any suitable
produce the desired diesel rather than a two step process in type of reactor. Suitable reactors include a fixed bed reactor
separate reactor vessels. Surprisingly, in the present inven and a slurry reactor. A fixed bed reactor has an advantage of
tion, a single catalyst can be used in contrast to a conventional easy separation of the reactants and products from the cata
two step process, which uses two different catalyst composi lyst. Fixed bed reactors include plug flow and trickle bed
tions, one for the HDO and one for HIHC. Furthermore, the 25 reactors. Fixed bed reactors can be of the type adiabatic,
steps of pretreatment of feed material and removal of impu multi-tubular, continuous recirculating packed bed reactor.
rities from the intermediate product, after HDO and prior to Slurry reactors include batch, a continuously stirred tank
HI/HC, can be eliminated. reactor, and a bubble column reactor. In the slurry reactors,
Hydrotreatment, as described in the present invention, the catalyst may be removed from the reaction mixture by
comprises contacting the feed with hydrogenatelevated tem 30 filtration or centrifugal action. Preferably, the process of this
peratures and pressures in the presence of the disclosed cata invention is a continuous process and the reactor is a fixedbed
lyst compositions, to hydrodeoxygenate, hydroisomerize or continuously stirred tank reactor. More preferably, the
and/or hydrocrack the feed into the desired fuel. Tempera process is a continuous process and the reactor is a fixedbed
tures range from 250 to 425°C., preferably at 300 to 400° C., reactOr.
most preferably from 325 to 375° C. Pressures range from 35 Preferably, the process is a continuous process in a fixed
500 to 2500 psig (3,450 to 17.250 kPa), preferably 1000 to bed or slurry reactor and the catalyst is in the form of particles,
2000 psig (6,900 to 13,900 kPa). preferably shaped particles. By “shaped particle' it is meant
In an alternative embodiment there is provided a process the catalyst is in the form of an extrudate. Extrudates include
for hydrodeoxygenation of a renewable resource which pro cylinders, pellets, or spheres. Cylinder shapes may have hol
cess comprises (a) providing a feed which is a renewable 40 low interiors with one or more reinforcing ribs. Trilobe, clo
resource; (b) contacting the feed with a catalyst in the pres Verleaf, rectangular- and triangular-shaped tubes, cross, and
ence of hydrogen at a temperature of 250 to 425° C. and a “C”-shaped catalysts can be used.
pressure of 500 to 2500 psig (3,450 to 17,250 kPa), wherein Preferably the shaped catalyst particle is about 0.01 to
the catalyst comprises one or more active metals selected about 0.5 inch (about 0.25 to about 13 mm) in diameter when
from the group consisting of nickel, cobalt, molybdenum, 45 a packed bed reactor is used. More preferably, the catalyst
tungsten and combinations of two or more thereof and a first particle is about/32 to about 4 inch (about 0.79 to about 6.4
oxide, wherein the catalyst is in reduced form, to produce a mm) in diameter.
hydrocarbon product having a ratio of odd-numbered hydro A wide range of Suitable catalyst concentrations may be
carbons to even-numbered hydrocarbons of at least 2:1, pref used. The amount of catalyst per reactor is generally depen
erably at least 3:1, more preferably at least 5:1 and most 50 dent on the reactor type. For a fixed bed reactor, the volume of
preferably at least 10:1. When the renewable resource com catalyst per reactor will be high, while in a slurry, the volume
prises over 50% Cis-based components, such as triglycer will be lower. Typically, in a slurry reactor, the catalyst will
ides, the process generally favors decarbonylation and/or make up 0.1 to about 30 wt % of the reactor contents. Pref
decarboxylation rather than hydrodeoxygenation. erably, the catalyst is 1 to 15 wt % of the reactor contents.
In a second alternative embodiment there is provided a 55 For a fixed bed reactor, the weight hourly space velocity
process for hydrodeoxygenation of a renewable resource will typically fall in the range of 0.05 to 100 hr', preferably,
which process comprises (a) providing a feed which is a 0.1 to 10 hr', more preferably 1.0 to 5.0 hr'.
renewable resource; (b) contacting the feed with a catalyst in In one embodiment of the process of the present invention,
the presence of hydrogen at a temperature of 250 to 425°C. the feed is contacted with hydrogen to form a liquid feed/
and a pressure of 500 to 2500 psig (3,450 to 17,250 kPa), 60 hydrogen mixture in advance of contacting the liquid feed/
wherein the catalyst comprises molybdenum and one or more hydrogen mixture with the catalyst. Optionally, a solvent or
active metals selected from the group consisting of nickel, diluent, having a relatively high solubility for hydrogen So
cobalt, or mixtures thereof and the catalyst is sulfided prior to that Substantially all the hydrogen is in solution, can be added
use, to produce a hydrocarbon product having a ratio of even to the feed and hydrogen in advance of contacting with the
numbered hydrocarbons to odd-numbered hydrocarbons of at 65 catalyst to form a liquid feed/solvent or liquid feed/diluent
least 2:1, preferably at least 3:1, more preferably at least 5:1 mixture. The liquid feed/solvent or liquid feed/diluent mix
and most preferably at least 10:1. Preferably, the catalyst ture is then contacted with hydrogen to form a liquid feed/
 US 8,084,655 B2
9 10
Solvent/hydrogen or liquid feed/diluent/hydrogen mixture. oil, oil sands or kerosene. (Light cycle oils can not be used as
The mixture containing hydrogen is then contacted with the a diesel fuel without the used of cetane enhancing additives.)
catalyst. The green diesel produced in this invention raises the cet
In a preferred process, the liquid feed/solvent/hydrogen or ane number without negatively impacting the density. Cetane
liquid feed/diluent/hydrogen mixture is contacted with cata numbers can be controlled by the selection of the specific
lyst in a packedbed reactor. Such as plug flow, tubular or other catalyst and the process conditions. Cetane numbers are
fixed bed reactor for feed and hydrogen to react. It should be desired to be in the range of 50 to 100, more preferably 70 to
understood that the packed bed reactor may be a single 100. The branching of some of the chains and the cracking
packed bed or multiple beds in series or in parallel or in a into Smaller chains lowers the cloud point temperatures that
combination thereofas discussed hereinabove. 10 would allow its usage in cold weather applications down to
The liquid feed/solvent/hydrogen or liquid feed/diluent/ -40° C., when blended in cold climate petro diesel. The
hydrogen mixture can be a Substantially hydrogen-gas-free degree of branching is dependent on the temperature of the
liquid feed stream. The feed stream can be produced by con application and can be controlled by the selection of the
tacting liquid feed with hydrogen and solvent or diluent to properties of the Zeolites used in the process and the type and
produce a hydrogen-saturated liquid feed. Alternatively or in
15 the combination of the metals. Green diesel produced by this
process also exhibit the desired lubricity (400 to 650
addition, after contacting liquid feed with hydrogen and Sol microns), viscosity (3 to 5 cSt at 40°C.), and density (750 to
vent or diluent, hydrogen gas can be removed from the feed 800 kg/m at 25°C.) suitable for today's diesel engines.
stream, for example, by known gas/liquid separation methods The present invention provides a process for more eco
in a disengagement step. Processes for producing hydrogen nomical production and implementation of green diesel with
gas-free liquid feed streams are known, Such as those dis little or no impact on current refining production facilities or
closed in U.S. Pat. Nos. 6,123,835; 6,428,686; 6,881,326 and current diesel engines.
7,291,257.
The percentage of hydrogen soluble in the solvent/diluent EXAMPLES
is greater than the percentage of hydrogen Soluble in the 25
liquid feed reactant. In this embodiment, preferably all of the Analytical Methods
hydrogen required for reaction is made available in Solution Samples were dissolved in chloroform and analyzed by
upstream of the fixed bed reactor, thus eliminating the need to GC/MS for peak identification and by GC/FID quantify the
circulate hydrogen gas within the reactor. individual components unless otherwise stated. For these
The reaction of liquid feed/solvent/hydrogen or liquid 30 examples, it is presumed the FID peak area 96 is equally
feed/diluent/hydrogen mixture with catalyst is highly exo comparable to weight percent due to the similarity of com
thermic and as a result a great deal of heat is generated in the ponents (all hydrocarbons, linear and branched). Peaks less
reactor. The temperature of the reactor can be controlled by than 0.1% were neither identified nor quantified hence the
using a recycle stream. A portion of the paraffin (hydrocar totals are 90% to 95% range. In Table 1, ethanol and a few
bon) product, (reactor effluent) can be recycled back to the 35 other minor impurities are contaminants in the chloroform
front of the reactor as a recycle stream and blended with fresh solvent. Most of the yield loss in all the examples, but espe
feed and hydrogen for use as solvent or diluent. cially in Examples 5 through 8, is due to evaporation of low
The process can be a multi-stage process using a series of boilers upon depressuring the reaction tubes and due to some
two or more reactors in series and fresh hydrogen can be residual product remaining in the tubes after the reaction was
added at the inlet of each reactor. The recycle stream absorbs 40 completed and the vessel was emptied.
Some of the heat and reduces the temperature rise through the Catalyst Sulfiding Procedure
reactor. The reactor temperature can be controlled by control A reactor consisting of 3/4" (19 mm) OD 31.6L Stainless
ling the fresh feed temperature and the amount of recycle. In Steel tubing 14" (36 cm) long was used for sulfiding catalyst.
addition, because the recycle stream comprises reacted com The reactor was packed with alternating layers of 1 mm glass
ponents, the recycle stream also serves as an inert diluent. 45 beads and PYREX wool at both ends, except in the middle,
The type and amount of diluent added, as well as the reactor where catalyst (10 to 30 g) was packed. The reactor had 3
conditions can be set so that Substantially all of the hydrogen thermocouples measuring the gas inlet, gas outlet, and cata
required in the hydrotreating reactions is available in Solu lyst bed temperatures. The reactor was placed in the vertical
tion. The solvent or diluent is preferably a portion of the tube furnace and the gas inlet and the gas outlet connections
reactor effluent used as a recycle stream, but can alternatively 50 were established. The catalyst was allowed to dry overnight at
be selected from the group consisting of light hydrocarbons, 130° C. with a 200 sccm of nitrogen flow. After drying the
light distillates, naphtha, diesel, or the like. Examples include catalyst, the oven temperature was increased at a rate of
propane, butanes, and/or pentanes. The percentage of hydro 0.5-1.0°C/minute and 20 sccm hydrogen sulfide (5% mix
gen in the solvent or diluent is greater than the percentage of ture in hydrogen) was added to the 200 sccm N, flow. Once
hydrogen in the feed, thus, in this embodiment, all of the 55 the temperature reached 190° C., the nitrogen flow was
hydrogen required for reaction is made available in Solution reduced to 100 sccm and the hydrogen sulfide flow was
upstream of the reactor and eliminating the need to re-circu increased to 30 sccm. The temperature was held at 240° C.
late hydrogen gas co-eluting with the effluent or product After 2 hours, the temperature was reduced slowly. Once the
Stream. temperature was below 125° C., the hydrogen sulfide flow
Green Diesel 60 was stopped but the nitrogen flow was maintained at 100 sccm
The process of this invention may be used to produce green until reactor reached room temperature (approx 25°C.). The
diesel. Green diesel produced in the process of this invention reactor was removed from the furnace and was unloaded in a
has the desired properties for use as diesel or for blending nitrogen purge box.
with petro diesel. The substantially linear product has a high Catalyst Reduction Procedure
cetane number, which is needed to maintain power for diesel 65 Similar equipment and set-up used for Sulfiding catalyst
engines to run efficiently. One can use the product as fuel was used for reducing the catalyst. The catalyst was dried
alone, or to blend in lower cetane products, such as light cycle overnight at 130° C. under a 200 sccm nitrogen flow. The
 US 8,084,655 B2
11 12
reactor had 3 thermocouples measuring the gas inlet, gas tion by weight: Cs—1%, Cs2%, C7-78%, C3%,
outlet, and catalyst bed temperatures. The reactor was placed C=11%, Ca.1%, Cal 4%. Some branching (<0.5 wt %
in the vertical tube furnace and the gas inlet and the gas outlet isoheptadecane, “iso-C, was observed.
connections were established. The catalyst was allowed to dry
overnight at 130°C. with a 200 sccm of nitrogen flow. After 5 Example 3
drying the catalyst, the oven temperature was increased at a
rate of 0.5-1.0°C/minute and 20 sccm hydrogen gas (99.0% The process of Example 2 was repeated using the same
purity) was added to the 200 sccmN flow. Once the tempera equipment, pressure and temperature conditions, and the
ture reached 190° C., the nitrogen flow was reduced to 100 reactants except for the catalyst and no Zeolite was added. The
sccm and the hydrogen flow was increased to 30 sccm. The 10
catalyst used was reduced nickel powder catalyst on Zirconia
temperature was held at 240°C. unless noted otherwise. For and kieselguhr (E-473P 2.5 g, available from BASF Cata
Comparative Examples B and D the temperature was lysts, Houston, Tex., USA). The reaction products were
increased to 250° C. and for Comparative Example C, the weighed (51 g). An IR spectrum showed no ester in the
temperature was increased to 350° C. After 2 hours, the tem sample. AGC-FID analysis gave the following linear paraffin
perature was reduced slowly. Once the temperature was 15
(hydrocarbon) distribution by weight: Cs=1%, C-2%.
below 125°C., the hydrogen flow was stopped but the nitro C-84%, C=1%, Cs—11%, C = 1%. Branching was not
gen flow was maintained at 100 scem until reactor reached observed.
room temperature (approx 25°C.). The reactor was removed
from the furnace and was unloaded in a nitrogen purge box. Example 4
Example 1 Example 2 was repeated using the same equipment, pres
Sure and temperature conditions. The reactants were the same
Soybean oil (100 g, available from Sigma-Aldrich Co., St. as in Example 2, but different amounts were used (100 g
Louis, Mo.) and a reduced Ni/NiO/MgO/SiO/graphite cata soybean oil, 5 g Ni 55/5 P catalyst, and 0.5g of USY zeolite
lyst (Pricat Ni 55/5 P. 5 g, available from Johnson Matthey, 25
powder, type EZ-190). AGC-FID analysis gave the following
West Deptford, N.J.) were placed in a 400cc agitated pressure product distribution by weight: n-Cs acid (octadecanoic
reactor. Soybean oil comprises triglycerides with the follow acid)=56%, n-Cs 9%, n-C, 29%, iso-C=1%,
ing distribution chain lengths: C-5%, Cal 5%, C-10%, n-C16=1%, n-C15=4%. The Example shows that the addition
Cs 3%, C-20%, Cs50%, Cs—7%. Cs refers to of Zeolite catalyst results in isomerized product, with low,
an 18 carbon chain with 1 unsaturated bonds, Cs refers to 30
10% zeolite present.
an 18 carbon chain with 2 unsaturated bonds, and Cs refers
to an 18 carbon chain with 3 unsaturated bonds. The autoclave Examples 5 Through 8
headspace was purged first with nitrogen 10 times by pres
surizing/depressurizing between 90 and 0 psig (722 and 101 Examples 5 through 8 illustrate hydrocracking and hydroi
kPa), then with industrial grade hydrogen (high pressure 99% 35 Somerization in a single step. Results from Examples 5
purity, available from GTS Inc., Morrisville, Pa., USA) 5 through 8 are summarized in Table 1 below. The Examples
times, and finally pressurized to 500 psig (3550 kPa) with used a feed comprised of a mixture of hydrocarbons: 3%
hydrogen. The autoclave and its contents were heated to 250° n-Co, 91% n-Cs, and 6% n-C2) prepared by hydrodeoxy
C. with agitation. The hydrogen pressure was increased to genating canola oil in a continuous flow reactor using a com
2000 psig (13,900 kPa), and maintained there for 5 hours. The 40 mercial nickel/molybdenum on alumina catalyst at a tem
headspace was filled with fresh hydrogen to 2000 psig (13. perature 325° C. and pressure 1500-2000 psig (10,400-13,
900 kPa) if the pressure dropped below 1500 psig (10.400 900 kPa), followed by distilling the product to obtain a
kPa). The temperature was maintained at 250+10°C. predominantly n-Cs cut.
The autoclave contents were then cooled to below 50° C., This feed mixture (100 g) was reacted with reduced
the headspace was vented, and the contents (103 g) were 45 Ni/NiO/MgO/SiO/graphite catalyst (Pricat Ni 55/5 P cata
discharged to a glass bottle. IR and HNMR analysis showed lyst) (2.5g) individually mixed with 4 different Zeolite pow
the presence of residual mono-, di- and triglycerides. A small ders (2.5 g), specified in Table 1. These Examples were con
sample was then transesterified using methanol and base cata ducted at 300° C. and 1500 to 2000 psig (13.900 kPa) under
lyst and the resulting sample was analyzed using GC-MS hydrogen in 400-cc pressure tubes for 5 hours under constant
(peak identification) and GC-FID (species quantification) to 50 shaking. Hauptake was less than those in Examples 1 through
show that the sample was equally divided among the methyl 4.
esters of the fatty acids (unreacted glycerides), alpha-olefins
and normal paraffins (hydrocarbons). Thus, the nickel cata TABLE 1
lyst hydrodeoxygenated the Soybean oil.
55 Zeolites and weight percent of products for Examples 5 through 8
Example 2 Example No.
Soybean oil (50 g) and the catalyst used in Example 1 were 5 6 7 8
placed in a 400 cc agitated pressure reactor. The reaction was Zeolite
run at 300° C. and the catalyst contained USY Zeolite powder 60
Mordenite Beta LZ-Y-84 USY
(0.125 g, type EZ-190, available from Engelhard (now part of Product Amount, g
BASF), Si/Al=3.05) physically mixed in. The reaction con
tents were weighed (51 g). The sample was base transesteri Product I.D. by GC/MS 87 82 42 48
fied. IR showed the sample to be pure hydrocarbon with a Isobutane 4.4 6.1 9.8 8.9
trace of ester. A proton NMR analysis showed that the ester 65 Isopentane 12.6 14.1 35.2 31.8
impurity was minute (<100 ppm). A GC-FID analysis gave Isohexane 12.9 14.5 37.1 34.8
the following linear paraffin (hydrocarbon) product distribu
 US 8,084,655 B2
13 14
TABLE 1-continued hydrotreating catalyst (5 g, CRI DC2318, commercially
available Criterion Catalysts and Technologies, Houston,
Zeolites and weight percent of products for Examples 5 through 8 Tex.) were placed in a 210 cc agitated pressure reactor. The
Example No. vessel was leaked check with nitrogen. The headspace of the
5 reactor was purged with nitrogen 10 times by pressurizing to
5 6 7 8 90 psig (722 kPa) and depressurizing to 0 psig (101 kPa). The
Zeolite reactor was then purged with high purity hydrogen (99.9%
Mordenite Beta LZ-Y-84 USY
min., commercially available from Air Products, Allentown,
Product Amount, g
Pa.) five times, and pressurized to 1000 psig (7000 kPa) with
10 hydrogen. The reactor and its contents were agitated and
Product I.D. by GC/MS 87 82 42 48 heated to 325° C. (617 F.). The hydrogen pressure was
increased to 2000 psig (13.900 kPa), and maintained there for
n-Heptane
2-Methylheptane
S.6
4.9
5.7
3.4
6.4 8.O
1.3
5 hours. The headspace was filled with fresh hydrogen to
3-Methylheptane 3.5 2.9 1.1 1500-1700 psig (11,800 kPa) if the pressure dropped below
3-Methyloctane 4.6 3.3 4.0 15
1000 psig (7000 kPa).
Ethanol 11.4 7.3 3.5 The reactor contents were then cooled to below 50° C.
2-Methylnonane 3.7 2.4 (122°F), the headspace was vented, and the contents were
p-Xylene O.1 O.1
Undecane discharged to a glass bottle. The contents were weighed (51
o-Xylene O.1 g). IR and "H NMR analysis showed no evidence of mono-,
Dodecane di- and triglycerides. The sample was then analyzed using
1,2,4-Trimethylbenzene
C3-Benzene
O.1
O.2
GC-MS (peak identification) and GC-FID (species quantifi
Tridecane O.2 cation) to show that the sample was converted to the following
Tetradecane linear paraffins (hydrocarbons) by weight: Cs-1%,
Tetradecane C14 Cs-81%, C7-6%, C-11.5%, C-0.5%. The Cs:C,
Pentadecane C15
Hexadecane C16 8.2 3.8 25
ratio is greater than 13:1 and Ce:Cs ratio is greater than
20:1.
Heptadecane C7 3.5 3.7
4-Ethyltetradecane 2.1 1.O
4-Methylhexadecane 0.7 O.3 Example 11
2-Methylheptadecane 0.4 O.2
4-Methylheptadecane 1.6 O.9 Example 10 was repeated using the same equipment, reac
Octadecane C1s 14.2 25.7 30
Nonadecane Co O.3 O.6 tion conditions, procedures and the reactant (50g), except for
different hydrotreating catalyst (5 g, alumina-Supported pre
Percent Totals 94.6 95.9 92.3 90.4 sulfided nickel/molybdenum bi-metallic hydrotreating cata
lyst, CRI DN-3330, commercially available Criterion Cata
As can be seen from table 1, linear hydrocarbons similar to 35
lysts and Technologies, Houston, Tex.). A GC-FID analysis
those produced in Examples 1 through 3, undergo hydroi of the product gave the following linear paraffin (hydrocar
Somerization and hydrocracking using catalysts comprising bon) product distribution by weight: Cs=1%, Cs 73%,
nickel Supported on alumina combined with a Zeolite. C=12%, C=10%, Cs-1.5%. There was also 2.5% of
n-octadecanoic acid in the product. The Cs: C, ratio is over
Example 9 6 and Ce:Cs ratio is over 7.
40
n-Octadecane feed (100 g, same as used in Examples 5 Example 12
through 8) and reduced Ni/NiO/MgO/SiO/graphite catalyst
(Pricat Ni 55/5 P catalyst, 2.5 g) were placed in a 400 cc Catalyst (5 g. CRI DC2318), temperature and pressure
agitated pressure reactor. The autoclave headspace was conditions were repeated from Example 10 except crude soy
purged first with nitrogen 10 times by pressurizing/depres 45 bean oil (50 g, obtained from Perdue Farms, Salisbury, Md.)
surizing between 90 and 0 psig (722 and 101 kPa), then with was used. The reaction products were analyzed by GC-FID to
industrial grade hydrogen (high pressure, 99% purity, avail obtain the following linear paraffin (hydrocarbon) distribu
able from GTS Inc., Morrisville, Pa.) 5 times, and finally tion by weight: Cs—0.5%, C-80%, C7-7%, C-11.6%,
pressurized to 500 psig (3550 kPa) with hydrogen. The auto Cs 0.9%. The Cs:C7 ratio is greater than 11:1 and Ce:Cs
clave and its contents were heated to 325°C. with agitation. 50 ratio is greater than 12:1.
The hydrogen pressure was increased to 2000 psig (13.900
kPa), and maintained there for 5 hrs. The headspace was filled Example 13
with fresh hydrogen to 2000 psig (13,900 kPa) if the pressure
dropped below 1500 psig (10.400 kPa). The temperature was Catalyst (5 g. CRI DC2318), temperature and pressure
maintained at 325-10° C.
The autoclave contents were then cooled to below 50° C.,
55 conditions were repeated from Example 10 using the same
the headspace was vented, and the contents (~100 g, includ equipment, pressure, and temperature, except for a refined,
ing the catalyst) were discharged to a glass bottle. A GC-FID bleached, and deodorized soybean oil sample (50 g, obtained
analysis gave the following linear paraffin (hydrocarbon) from Perdue Farms, Salisbury, Md.) was used. The reaction
product distribution by weight: C-3%, Cs 84%, products were analyzed by GC-FID to obtain the following
C7–13%. Note that the catalyst seemed to have converted 60 linear paraffin (hydrocarbon) distribution by weight: Cs
Some n-Cs to n-C7 through hydrocracking, but did not cause =0.5%, C-79%, C-8%, C-11.3%, C=1.2%. The Cs:
any isomerization. C7 ratio is almost 10, and Ce:Cs ratio is greater than 9.
Example 10 Example 14
65
Soybean oil from Sigma-Aldrich, 50 g, and alumina-Sup The process of Example 13 was repeated using the same
ported pre-sulfided cobalt/nickel/molybdenum tri-metallic equipment, pressure, temperature, and catalyst (5 g), except
 US 8,084,655 B2
15 16
refined coconut oil, (50g, obtained from Spectrum Chemicals Comparative Example B
of Gardena, Calif.) was used. The reaction products were
analyzed by GC-FID to obtain the following linear paraffin The process of Example 18 was repeated using the same
(hydrocarbon) distribution by weight: Cs=9%, C7-1%, equipment, pressure, except the temperature was 500° C.
C=9%, C-1%, C-17.5, C-2, C-43.5%, C-4, Grace-Davidson AT535 catalyst (5 g), and crude soybean oil
Co-5.5, C-0.5, C-6.5%, C, 0.5%. The Cs:C, ratio is from Perdue Farms (50 g) was used. The catalyst was
approximately 9, Ce:Cs ratio is 9, Ca:C ratio is approxi reduced, as described herein above. No reaction occurred.
mately 9, CC ratio is approximately 11, Co.:C ratio is Example 19
11, and Cs: C, ratio is 13. 10
Example 15 The process of Example 18 was repeated using the same
equipment, pressure, and temperature except the catalyst was
The process of Example 13 was repeated using the same Grace-Davidson AT 535 catalyst (5 g) and crude soybean oil
equipment, pressure, temperature, and catalyst (5 g), except from Perdue Farms (50 g) was used. The catalyst was sul
palm oil (50g, manufactured by T.I. International Ghana Ltd. 15 fided, as described hereinabove. The reaction products were
of Accra, Ghana) was used. The reaction products were ana analyzed by GC-FID to obtain the following linear paraffin
lyzed by GC-FID to obtain the following linear paraffin (hy distribution by weight: Cs2.0%, Cs 78.0%, C7-8%,
drocarbon) distribution by weight: C =0.5%, Cs, 46.5%, C=10%, Cs-1.1% C, 0.2%, C-0.2%, C=0.1%,
C75%, C-43%, Cs 4%, Ca.1%. The Cs:C, ratio is C=0.1%, Cz-o-0.3%. The Cs:C, ratio is approximately
greater 9, and Ce:Cs ratio is greater than 10. 9.75, and Ce:Cs ratio is greater than 9.
Example 16 Comparative Example D
The process of Example 13 was repeated using the same The process of Example 18 was repeated using the same
equipment, pressure, temperature, and catalyst (5 g), except 25 equipment, pressure, and temperature, except the catalyst was
chicken fat (50 g, obtained from Perdue Farms of Salisbury, alumina-Supported non-sulfided nickel/cobalt/molybdenum
Md.) was used. The reaction products were analyzed by GC tri-metallic hydrotreating catalyst, (5 g, AT 592, from Grace
FID to obtain the following linear paraffin (hydrocarbon) Davidson, Columbia, Md.), and crude soybean oil (50 g,
distribution by weight: Cs=1%, C-60%, C-7%, obtained from Perdue Farms, Salisbury, Md.) was used. The
C-28%. Cis-3%, Ca.1%. The Cs: C, ratio is approxi 30 catalyst was reduced, as described hereinabove. No reaction
occurred.
mately 9, and Ce:Cs ratio is greater than 9.
Example 17 Example 20

D100824-67 Stearic Acid, CRI Catalyst DC-2318 35 The process of Example 19 was repeated using the same
equipment, pressure, and temperature except Grace-David
The process of Example 13 was repeated using the same son AT 792 catalyst (5 g) was used. The catalyst was sulfided,
equipment, pressure, temperature, and catalyst (5 g), except as described hereinabove. The reaction products were ana
stearic acid (50 g, from VWR, West Chester, Pa.) was used. lyzed by GC-FID to obtain the following linear paraffin dis
The reaction products were analyzed by GC-FID to obtain the 40 tribution by weight: Cs=1.8%, Cs—82.4%, C, 3.3%,
following linear paraffin (hydrocarbon) distribution by C=11.2%, C-0.5%, C-0.2%, C-0.1%, C=0.1%,
weight: C =0.7%, Cs 90.4%, C7-8.4%, C-0.5%. The C=0.1%, Cz-o-0.3%. The Cs:C, ratio is approximately
Cs: C, ratio is approximately 10.8. 25, and Ce:Cs ratio is greater than 22.
As can be seen from Examples 10-20 and Comparative
Example 18 45 Examples A-D, the cobalt/nickel/molybdenum and nickel/
molybdenum catalysts produced higher ratio of even-num
The process of Example 13 was repeated using the same bered hydrocarbons to odd-numbered hydrocarbons.
equipment, pressure, temperature, and catalyst (5 g), except a
50:50 chicken fat to soybean oil mixture (50 g, mixed in What is claimed is:
house with chicken fat and soybean oil obtained from Perdue 50 1. A process for hydrotreating a liquid feed comprising
Farms of Salisbury, Md.) was used. The reaction products (a) providing a liquid feed which is a renewable resource
were analyzed by GC-FID to obtain the following linear comprising aliphatic hydrocarbon chains having C to
paraffin (hydrocarbon) distribution by weight: Cs2.1%, Co. moieties; and
C-69.6%, C=7.2%, C-18.5%, C=1.9%, C-0.5%, (b) contacting the feed with a catalyst in the presence of
C=0.1%, C-0.1%. The Cs: C, ratio is approximately 55 hydrogen at a temperature of 250 to 425° C. and a
9.7, and Ce:Cs ratio is greater than 2.5. pressure of 500 to 2500 psig (3.450 to 17,250 kPa) such
that isomerization and hydrocracking occur to produce a
Comparative Example A paraffin (hydrocarbon) product,
wherein the catalyst comprises one or more active metals
The process of Example 18 was repeated using the same 60 Selected from the group consisting of nickel, cobalt, and
equipment, pressure, except the temperature was 400°C., the combinations thereof and a first oxide selected from the
catalyst was alumina-Supported non-sulfided nickel/molyb group consisting of alumina, Silica, titania, Zirconia, kie
denum bi-metallic hydrotreating catalyst, (5 g, AT 535, from Selguhr, silica-alumina, and combinations thereof, and a
Grace-Davidson, Columbia, Md.), and crude soybean oil (50 second oxide wherein the second oxide comprises a
g, obtained from Perdue Farms, Salisbury, Md.) was used. 65 Zeolite and wherein the Zeolite is present in an amount of
The catalyst was reduced, as described hereinabove. No reac at least 10 wt %, based on the total catalyst weight, and
tion occurred. wherein the first oxide is used as a support for the active
 US 8,084,655 B2
17 18
metal and wherein the second oxide is physically mixed 11. The process of claim 1 wherein the Zeolite is selected
with the active metal and the first oxide. from the group consisting of MFI (ZSM-5), MEL (ZSM-11),
2. The process of claim 1 wherein the feed is an oil derived FAU (zeolite Y or USY), MOR (mordenite), BEA (beta).
from plants and/or animals and comprises one or more trig 12. The process of claim 1 wherein the Zeolite is present in
lyceride. an amount of 25-50 wt %.
3. The process of claim 2 wherein the triglyceride is 13. The process of claim 1 wherein the temperature is 300
to 400° C.
derived from a plant selected from the group consisting of 14. The process of claim 13 wherein the temperature is 325
pine, rape seed, Sunflower, palm, jathropa, seashore mallow to 375o C.
and combinations of two or more thereof. 15. The process of claim 1 wherein the pressure is 1000 to
10
4. The process of claim 1 wherein the feed is a vegetable oil 2000 psig (7000 to 13,900 kPa).
selected from the group consisting of canola oil, palm oil, 16. The process of claim 1 wherein the process is a con
coconut oil, palm kernel oil, Sunflower oil, Soybean oil, crude tinuous process and the reactor is a fixed bed reactor or a
tall oil, and combinations of two or more thereof. continuously stirred tank reactor.
5. The process of claim 1 wherein the concentration of 15 17. The process of claim 16 wherein the reactor is a fixed
metal in the catalyst is 45 to 60 weight percent. bed reactor.
6. The process of claim 5 wherein the catalyst comprises 18. The process of claim 16 wherein the feed is contacted
nickel which is in reduced form. with a solvent or diluent and hydrogen to provide a liquid
7. The process of claim 6 wherein the catalyst is reduced by feed/solvent/hydrogen or liquid feed/diluent/hydrogen mix
treating the catalyst with hydrogen at a temperature from ture in advance of contacting the feed with the catalyst.
100° C. to 400° C. 19. The process of claim 18 wherein a portion of the prod
8. The process of claim 6 wherein the Zeolite is present in uct is recycled back to the reactor as a recycle stream and
an amount of at least 25 wt %, based on the total catalyst blended with fresh feed and hydrogen for use as solvent or
weight. diluent.
9. The process of claim 7 wherein the Zeolite is present in 25 20. The process of claim 17 wherein the liquid feed/sol
an amount of 25-50 wt %, based on the total catalyst weight. Vent/hydrogen or liquid feed/diluent/hydrogen mixture is a
Substantially hydrogen-gas-free liquid feed stream.
10. The process of dam 6 wherein the renewable resource
comprises over 50% Cis-based components. k k k k k