US008912375B2

(12) United States Patent (10) Patent No.: US 8,912,375 B2

Egeberg et al. (45) Date of Patent: Dec. 16, 2014
(54) HYDROCONVERSION PROCESS AND USPC ............... 585/240; 585/242: 44/605; 44/606:
CATALYST 502/255
(75) Inventors: Rasmus Gottschalck Egeberg, (58) Field of Classification Search
Fredensborg (DK); Kim Gron Knudsen, CPC ............... C1OL 5/40; C1OL 5/44; C1OL 9/04;
Hellerup (DK); Niels Jorgen Blom, C10G 3/42; C10G 3/46; C10G 3/50; C10G
Hillerød (DK); Jens A. Hansen, Holte 45/04; C10G 45/08; C10G 47/10; C10G
(DK) 2300/1011: C10G 2300/1018; C10G
2300/1048; C10G 2400/04
(73) Assignee: Haldor Topsoe A/S, Lyngby (DK) USPC .............. 585/240, 242:44/605, 606: 502/255
See application file for complete search history.
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 (56) References Cited
U.S.C. 154(b) by 952 days. U.S. PATENT DOCUMENTS
(21) Appl. No.: 13/063,107 4,225,421 A 9/1980 Hensley, Jr. et al.
4.294,685 A 10, 1981 Kim et al.
(22) PCT Filed: Jul. 23, 2009 4,526,675 A * 7/1985 Mahoney et al. ............. 208/106
4,552,650 A * 1 1/1985 Toulhoat et al. ........ 208,216 PP
(86). PCT No.: PCT/EP2O09/OOS346 4,992,605 A 2/1991 Craig et al.
6,919,294 B2 7/2005 Saito et al.
S371 (c)(1), 8,142,527 B2* 3/2012 Herskowitz et al. ............ 44f605
(2), (4) Date: Mar. 9, 2011 8,258,074 B2* 9/2012 Romero et al. ........ ... 502/313
8,435,912 B2* 5/2013 Chaumonnot et al. ........ 502,158
2004/O126315 A1 7/2004 Saito et al.
(87) PCT Pub. No.: WO2010/028717 2004/0230085 A1 11/2004 Jakkula et al.
PCT Pub. Date: Mar. 18, 2010 2006/0186O20 A1* 8/2006 Gomes ............................ 208.46
2008. O161614 A1* 7/2008 Bertoncini et al. 585,240
(65) Prior Publication Data 2009/O166256 A1* 7/2009 Lewis et al. ..................... 208/89
2009/O193709 A1* 8/2009 Marker et al. .................. 44, 308
US 2011/O166396 A1 Jul. 7, 2011
FOREIGN PATENT DOCUMENTS
(30) Foreign Application Priority Data
CN 1010292.45 A 9, 2007
EP 1741 767 A1 1, 2007
Sep. 10, 2008 (DK) ................................. 2008 O1267 WO WOO2,32570 A2 4/2002
WO WO 2007 141293 A1 12/2007
(51) Int. Cl.
CD7C I/00 (2006.01) * cited by examiner
BOI 2L/00 (2006.01)
CIOL L/04 (2006.01) Primary Examiner — Nina Bhat
CIOG 45/02 (2006.01) (74) Attorney, Agent, or Firm — Dickstein Shapiro LLP
CIOG 45/58 (2006.01)
CIOG 65/04 (2006.01) (57) ABSTRACT
CIIC3/00 (2006.01) A process and hydrodeoxygenation catalyst for producing
CIOG 3/00 (2006.01) high-quality diesel and naphtha fuels from a feedstock that
(52) U.S. Cl. contains oxygen containing components derived from renew
CPC. CI0L I/04 (2013.01); C10G 45/02 (2013.01); able organic material in which the hydrodeoxygenation cata
CI0G 45/58 (2013.01): CI0G 65/043 lyst is a Supported Mo catalyst and in which the Support has a
(2013.01): CI IC3/00 (2013.01): CI0G 3/44 bimodal porous structure. The hydrodeoxygenation catalyst
(2013.01): CI0G 3/48 (2013.01); C10G 3/50 has a Mo content of 0.1 to 20 wt %. The support is alumina,
(2013.01); Y02E 50/13 (2013.01); CIOG silica, titania or combinations thereof, and the Support has a
2300/1014 (2013.01); C10G 2300/1018 bimodal porous structure with pores with a diameter larger
(2013.01); C10G 2300/4081 (2013.01); CIOG than 50 nm that constitute at least 2 vol% of the total pore
2300/4018 (2013.01); C10G 2300/207 Volume.
(2013.01); C10G 2400/02 (2013.01); CIOG
2400/04 (2013.01) 13 Claims, No Drawings
 US 8,912,375 B2
1. 2
HYDROCONVERSION PROCESS AND (as evidenced by the formation of H2O and n-Cs) or a com
CATALYST bination hereof. The yield of high-boiling components was
greatly enhanced when using a catalyst impregnated with a
This application is a national stage entry of PCT/EP2009/ hydrogenating function, compared to a strictly thermal pro
005346, filed on Jul. 23, 2009. cess or compared to a process employing a silica-alumina
This invention relates to a catalytic conversion process catalyst with no impregnated metals. The hydrocracking
involving the use of hydrogen, hydrocarbons, particularly reactions convert the higher hydrocarbons into gasoline and
renewable organic materials such as Vegetable and animal oils gas, thereby lowering the diesel yield of the process.
and components derived therefrom. More particularly, the In an article by J. Gusmão and co-workers (Cat. Today, 5
invention is related to a process and hydrodeoxygenation 10
(1989) 533-544) the conversion of vegetable oil over a tradi
catalyst for producing high-quality diesel and naphtha fuels tional sulfided Ni Mofalumina hydrotreating catalyst is
from a feedstock that contains oxygen containing compo described. At a pressure of 200 bar, the conversion of soy oil
nents derived from renewable organic material. The invention into hydrocarbons was reported to initiate at 300° C. and be
relates also to the use of a supported Mo catalyst in which the
Support has a bimodal porous structure. 15 complete at 360° C. The normal alkanes in-Cs, n-C, n-Cz,
Hydrotreating of hydrocarbons at the refinery allows large and n-Cs constituted 96 mol % of the products and were
scale transformation of crude oil fractions and intermediary formed by a combination of decarbonylation, decarboxyla
refinery stream into clean transportation fuels meeting regu tion and hydrogenation. Isomerization and hydrogenolysis
latory specifications. The hydrotreating process removes Sul was not observed.
fur and nitrogen by reaction with hydrogen and can also U.S. Pat. No. 4,225,421 and WO-A-02/32570 describe the
change the structure of petroleum hydrocarbons e.g. by use of molybdenum catalysts Supported on bimodal alumina
hydrocracking reactions. for hydrodemetallation and hydrodesulfurisation of heavy
Renewable organic material is an alternative source of hydrocarbons. U.S. Pat. No. 4.294,685 describes the use of a
energy that can Supplement fossil fuels. Vegetable oils and molybdenum catalyst Supported on bimodal alumina for the
animal fats consist mainly (typically >95 wt %) of triglycer 25 hydroconversion of coal Solids in solvent (coal liquefaction).
ides, having the following general formula: U.S. Pat. No. 5,705,722 teaches the use of a hydroprocess
ing catalyst to convert a tall oil feedstock into a mixture of
compounds, some of which can be used as diesel fuel addi
O tives. The process takes place attemperatures above 350° C.
CH-O-C-R1
30 Similarly, U.S. Pat. No. 4,992,605 describes the conversion of
O canola oil, Sunflower oil, soybean oil, rapeseed oil, palm oil
and fatty acid fraction of tall oil into mainly Cs-Cs hydro
HC-O-C-R2 carbons using a hydroprocessing catalyst at 350-450° C. The
O high temperatures applied in these processes cause conver
CH-O-C-R3
35 sion of diesel-range material into naphtha.
Patent Application FI960525 describes a two step process
where vegetable oil is converted to middle distillates that can
The groups R1, R2 and R3 are aliphatic chains, which be used as a diesel fuel. The feed is first hydrogenated to yield
typically contain 7-24 carbon atoms and 0-3 double bonds. normal paraffins in a hydrotreating step using a conventional
The oils may also contain a fraction of free fatty acids with 40 hydroprocessing Ni Mo or Co-Mo catalyst and in the
similar chain lengths and degree of unsaturation. If crude tall second step is isomerized to branched paraffins by the use of
oil or tall oil derived material is used then the feedstock can a Supported group VIII element catalyst.
also contain resin acids. Fatty acid esters (e.g. obtained by U.S. Patent application 2004/0230085A1 describes a two
transesterification of triglycerides with an alcohol), in par step process comprising a hydrodeoxygenation (HDO) step
ticular fatty acid methyl esters (biodiesel) and other oxygen 45 and an isomerization step, the latter being operated Such that
containing material derived from renewable organic material hydrogen and liquid feed are contacted by using a counter
can also be used as a feedstock, and processed similar to raw current flow principle. HDO catalysts include Pd, Pt, Ni,
Vegetable oils and animal fats. NiMo or CoMo catalysts, the support being alumina and/or
In order to use feedstocks derived from renewable organic silica.
material in conventional automobile engines it is desirable to 50 The prior art suffers from a lack of reaction control in the
convert the material into hydrocarbons that are similar to top part of the hydroprocessing reactor. As the reaction of
those present in fossil derived transportation fuels. It has Vegetable and/or animal oils with hydrogen is a highly exo
already for a number of years been known how to convert thermic process that consumes high amounts of hydrogen, the
Vegetable oils into normal paraffins in the gasoline or diesel temperature can rise very rapidly in the top of the reactor and
boiling range by employing a hydrotreating process. In this 55 the hydrogen partial pressure may be very low at the active
process the renewable organic material is reacted with hydro reaction sites on the catalyst. These conditions will lead to
genatelevated temperature and pressure in a catalytic reactor. coke formation, plugging up the catalyst and cause a high
In the thesis “HYDRCRAQUAGE DE L'HUILE DESOJA pressure drop as well as to increased deactivation rate of the
SUR DES CATALYSEURS AU RHODIUM ET AU catalyst.
RUTHENIUM SUPPORTES” by P.P. Nunes, Université 60 Hence, it is an object of the invention to provide an
Pierre et Marie Curie, Paris, 1984, the reaction of soy oil with improved process and catalyst that enables the user to convert
hydrogen over silica- and alumina-Supported catalysts is the components derived from renewable organic material in
described. The triglycerides of soy oil were observed to the feedstock into hydrocarbons in the diesel boiling range
decompose into fatty acids, and Subsequently the fatty acids with low pressure drop and with a low catalyst deactivation
would either be hydrocracked (as evidenced by the formation 65 rate.
of light hydrocarbons), decarboxylated (as evidenced by the It is another object of the invention to develop a process that
formation of n-Cs, n-C7, CO and CO) or hydrogenolysed allows for a gradual conversion of the vegetable and/or ani
 US 8,912,375 B2
3 4
mal oils, thereby extending the effective reaction Zone and and at a liquid hourly space velocity of 0.1-10 h". In this
Suppressing the formation of carbonaceous deposits on the HDO step the pressure may preferably vary between 10 and
catalyst. 150 bars, more preferably between 20 and 100 bars and the
It is a further object of the invention to be able to use a inlet temperature varies between 200 and 350° C., preferably
catalyst that is effective in converting the oxygenates in the between 250 and 350°C. The conversion of biological mate
feed into hydrocarbons in the diesel boiling range, said cata rial to hydrocarbons in this step is above 50%, preferably
lyst being more resistant than the prior art catalysts to the above 70%. The H/oil ratio is preferably in the range 200
deposition of carbonaceous materials within the catalyst. 300 250 Nm/m.
Surprisingly, it has been found that an unpromoted catalyst The catalyst employed in the hydrodeoxygenation (HDO)
being impregnated only with Mo (and not Co or Ni) is effec 10 step of the process has a Support (carrier) with a bimodal pore
tive in converting vegetable oils, animal fats, fatty acids and distribution, i.e. having both pores with diameter below 50
fatty acid methyl esters into normal paraffins. As this catalyst nm and pores with diameter above 50 nm, as measured by
turns out to have a somewhat lower activity than traditional mercury intrusion porosimetry. The pore Volume constituted
Ni Mo or Co-Mo catalysts, the temperature increase and by pores with a diameter above 50 nm (macropores) should
hydrogen partial pressure reduction due to the hydrogenation 15 constitute at least 2% of the total pore volume, preferably at
reactions take place in a larger section of the reactor, thereby least 10%, more preferably at least 15%.
minimizing the potential for forming coke and other deposits Without being bound to any specific theory, it is conjec
that damage catalyst activity and cause increased pressure tured that the existence of macropores, which as used herein
drop. By using a carrier with a bimodal pore distribution the comprise pores with pore diameters larger than 50 nm,
catalyst employed in the process is more resistant to pore ensures that the carbonaceous deposits and coke precursors
plugging and minimizes increases in pressure drop and deac that may form during the conversion of biological material
tivation rate. can diffuse out of the catalyst pellets and do not cause imme
Accordingly, we provide a process for production of a diate plugging of the pores. The diffusion of reacting mol
hydrocarbon fuel from renewable organic material of biologi ecules through the catalyst pellet may also proceed through
cal origin comprising the steps: 25 these large pores even in the case of moderate coke formation.
(a) forming a feedstock by combining a fossil hydrocarbon On the other hand, the existence of mesopores, which as used
fuel with a renewable organic material wherein the content herein comprise pores with pore diameters smaller than 50
of renewable organic material is 1 to 35 vol%; nm ensures a reasonably high Surface area and high metal
(b) mixing the feedstock of step (a) with a hydrogen-rich gas dispersion.
and conducting the combined stream to a hydrodeoxygen 30 Preferably, the content of renewable organic material in the
ation stage by contacting said combined stream with a feedstock is 10 to 30 vol%, more preferably 15 vol%, for
hydrodeoxygenation catalyst, wherein the hydrodeoxy instance 15 vol% rapeseed oil mixed with 85 vol% fossil
genation catalyst is a Supported Mo catalyst having Mo LGO; or 25 vol%, for instance 25 vol% FAME (biodiesel)
content of 0.1 to 20 wt %, the support being selected from and 75 vol% LGO.
alumina, silica, titania, and combinations thereof, and said 35 The metal component of said HDO-catalyst is molybde
Support having a bimodal porous structure with pores with num only. The catalyst with only Mo has low activity for
a diameter larger than 50 nm that constitute at least 2 vol% hydrodesulfurisation yet unexpectedly it is still active for
of the total pore volume. bio-fuel HDO (bio-fuel hydrogenation). The content of Mo is
The content of Mo in the catalyst is defined on a dry weight between 0.1 and 20 wt %, preferably between 0.1 and 10 wit
basis. 40 %, with alumina as the preferred support material. In com
The hydrogen-rich gas is preferably a hydrogen-recycle parison to promoted hydrotreating catalysts in their active
gas stream, a hydrogen make-up gas or a combination of both. sulfided phase (e.g. Ni Mo—S or Co Mo—S) the activity
As used herein the term “renewable organic material' is of Mo in its sulfided state (MoS) for most hydrogenation
used interchangeably with the term “renewable organic mate reactions is quite low.
rial of biological origin” and defines Vegetable oils, animal 45 For conventional hydrotreating processes, a low catalytic
fats, tall oil, and derived material such as fatty acid alkyl activity is not desired since larger reactor Volumes are needed
esters, particularly fatty acid methyl esters (FAME)—also to obtain the required degree of e.g. desulfurization. In the
known as biodiesel , or combinations thereof. All of these present invention and contrary to conventional thinking a low
represent renewable sources. Vegetable oils include rapeseed, catalytic activity is pursued while we still are able to obtain
Soybean, corn, coconut, palm and cotton oils. Animal fats 50 the same conversion of biological material into hydrocarbon.
include bacon grease, yellow grease, lard, butter and tallow. High hydrogenation activity can result in very high hydrogen
As used herein hydrodeoxygenation (HDO) means the consumption and a very high temperature increase over a
removal of oxygen of the fossil hydrocarbon fuel and/or small fraction of the active catalyst in the top of the reactor.
renewable organic material by means of hydrogen, i.e. fuel or This can lead to rapid catalyst deactivation and a permanently
bio-fuel hydrogenation. 55 higher pressure drop over the catalyst bed, which may force a
As used herein, hydroprocessing includes oil refinery pro premature shutdown of the unit in order to replace the cata
cesses which require the presence of hydrogen, Such as lyst.
hydrodeoxygenation (HDO), hydroisomerisation, By using a less active catalyst but still obtaining the same
hydrodearomatisation (HDA) and hydrotreatment such as in conversion of biological material into hydrocarbon, the same
particular hydrodesulfurisation (HDS) and hydrodenitrifica 60 amount of hydrogenis consumed in this reaction and the same
tion (HDN). absolute temperature rise will be seen. However, the conver
Thus, a gas containing hydrogen and the liquid feedstock sion will occur over a larger reactor Volume so that the place
that consists of vegetable and/or animal oils mixed with a where the local hydrogen partial pressure is low is not the
fossil-derived hydrocarbon component is passed to a reactor same as the place where the local hydrogen consumption is
with one or more hydrodeoxygenation (HDO) catalyst beds. 65 high. Thereby, the potential formation of coke particles that
The hydrodeoxygenation step (b) is carried out at a hydro inhibit catalyst activity and can cause pressure drop is mini
gen pressure of 1-200bars and at a temperature of 50-350° C. mized. The larger reaction Volume used also allows for at
 US 8,912,375 B2
5 6
better temperature control e.g. by quenching with cold hydro step (b) is simply passed without hydrotreatment to the
gen gas before the combined liquid and gas enters the second hydroisomerization step (d). We have found that it is possible
bed of the reactor. Furthermore, the low catalyst activity to substantially lower the cloud and pour points of hydrode
means that less hydrogen will be consumed in the event of e.g. oxygenated product even when processing Such a high-Sulfur
hydrodearomatization and hydrodesulfurization reactions feed, meaning that the catalyst of the present invention is also
compared to a traditional high-activity hydrotreating catalyst active when used for cold flow improvement in an HS atmo
again giving a higher hydrogen partial pressure that will sphere.
inhibit coke formation. The hydroisomerization step is preferably carried out by
Although the HDO reaction resembles HDS since in both mixing the liquid effluent from the first step (hydrodeoxygen
reactions a heteroatom is hydrogenated and taken out of the 10 ation) or second step (hydrotreating) of the process with a
molecule, the HDO catalyst of the invention only containing hydrogen rich gas and contacting the mixed stream with a
Mo is unexpectedly active in the conversion of triglycerides hydroisomerization catalyst. More preferably, the hydroi
despite being inactive in e.g. HDS, HDN. Somerization step is carried out by contacting the liquid prod
A number of procedures may be employed for preparing uct obtained from step a) or from step b) concurrently with a
the alumina Support. The large pores can be retained by only 15 hydrogen-containing gas stream over the hydroisomerization
adding no or only a small amount of acid to the alumina paste catalyst.
or by decreasing the effective residence time in the mixing In yet another embodiment the process further comprises
device. Large pores can also be formed by other techniques separating the effluent from any of the steps (b), (c) and (d)
known to those skilled in the art, Such as by grinding the into a liquid effluent stream and a gaseous effluent stream,
alumina and then binding the particles together into spheres mixing said liquid effluent stream with a fresh hydrogen-rich
or extrudates. Other techniques could be to employ pore gas, forming a purified hydrogen containing gas stream by
growth promoters e.g. by heating the material in the presence removing HS, NH, CO, CO and light hydrocarbons from
of a gas or metal compound, Steaming at elevated tempera said gaseous effluent, and recycling said purified hydrogen
tures or the like. In another preparation method, the large containing gas to any of the steps (b), (c) and (d).
pores may beformed during preparation of the alumina by the 25 The hydroisomerization treating catalyst of step (d) com
use of a strong acid for leaching. Still another procedure prises a metal component selected from Group VIII and/or VI
would be to introduce into the alumina structure, a material of the Periodic System and being supported on a carrier
which can later be removed to form the large pores. containing alumina, silica, titania, silica-alumina, ZSM-5,
Since the Mo catalyst employed in the HDO-step of the Zeolite beta or combinations thereof. Preferably the hydroi
process has a rather low desulfurization activity it may be 30 Somerization catalyst is Ni W Supported on a carrier con
necessary to hydrotreat the effluent in a second step using a taining alumina, Zeolite beta and silica-alumina.
conventional hydrotreating catalyst in order to obtain a prod This step may be carried out in the same reactor and/or
uct that meets specifications for diesel fuels. It may also be same catalyst bed as the previous step(s) or it may be carried
necessary to convert the remaining biological material to out in a separate reactor, as defined in Sub-claim 9. In a
hydrocarbons in this step. Accordingly the process of the 35 particular embodiment steps (b), (c) are carried out in the
invention may further comprise a step (c): passing the effluent same hydroprocessing reactor with step (b) being conducted
stream from step (b) to a hydrotreating stage by contacting in the top 20 vol% of the catalyst bed and step (c) in the
said stream with a hydrotreating catalyst. bottom 80 vol% of the catalyst bed. The catalyst bed is
This objective can be reached by a conventional therefore a combination of catalysts active in hydrodeoxy
hydrotreating step that normally involves operation at tem 40 genation (HDO) and hydrotreatment (HDS, HDN).
peratures between 200 and 500° C. and pressures up to 200 The hydroisomerization step involves operation between
bars. The H/oil ratio is preferably in the range 200-300 250 200 and 500° C. at pressures up to 200 bars. In a particular
Nm/m. The hydrotreating catalyst of step (c) comprises a embodiment, the hydrodetreating step (c) and hydroisomer
metal component selected from Group VIII and/or VI of the ization step (d) are carried out at a hydrogen pressure of 1-200
Periodic System and being Supported on a carrier containing 45 bar and at a temperature of 50-450° C., preferably at a pres
alumina, Silica, titania or combinations thereof. These cata sure of 10-150 bar and a temperature of 250-410°C. and at a
lysts are preferably those employed conventionally, Such as liquid hourly space velocity of 0.1-10 h". The H/oil ratio is
mixed cobalt and/or nickel and molybdenum sulfides (Co preferably in the range 200-300 250 Nm/m.
Mo, Ni Mo, Ni W) supported on alumina, silica, silica The hydroisomerization catalyst converts the normal par
alumina or combinations of these. Most preferably the 50 affins (created in the hydrogenation of the components
hydrotreating catalyst is Ni-Molalumina, Co-Molalumina derived from renewable organic material in the feedstock)
or Ni W/alumina. into iso-paraffins with better cold-flow properties. The
The renewable organic material is preferably selected from bifunctional hydroisomerization catalyst contains both acidic
triglycerides, fatty acids, resin acids, fatty acid esters or com sites typically associated with the oxide carrier and hydroge
binations thereof. 55 nation sites typically associated with the metal component. If
In an third part of the process, a hydroisomerization cata the active metal component is one or more Group VIII noble
lyst may be included to improve the cold flow properties of metals, the hydroisomerization should preferably be carried
the liquid product. Since the hydrogenation of vegetable and/ out in a separate reactor or catalyst bed and the feed to the
or animal oil mainly results in normal paraffins that have poor hydroisomerization catalyst should be virtually free of nitro
cold flow properties it may be necessary to decrease e.g. the 60 gen and Sulfur species, i.e. contain less than 100 wtppm Sulfur
cloud or pour point in order to meet regulatory specifications. and less than 100 wtppm nitrogen, preferably less than 10
Accordingly, the process of the invention may further com wtppm sulfur and less than 10 wtppm nitrogen. If the active
prise a step (d): passing the effluent stream from step (b) or (c) phase of the metal components is a metal Sulfide (e.g.
to a hydroisomerization stage by contacting said stream with Ni Mo—S. Co-Mo-S, Ni W S) then the step may be
a hydroisomerization catalyst. 65 carried out in a sour environment and the costly installment of
Thus, according to the invention the hydrotreating step (c) equipment to remove HS and NH formed in the previous
may be omitted and the effluent from the hydrodeoxygenation step(s) is thus not necessary.
 US 8,912,375 B2
7 8
The invention encompasses also as defined in claim 13 the of the fossil LGO is 405°C. Furthermore, the yield of propane
use of a hydrodeoxygenation catalyst in the form of a Sup was measured to be 0.65 wt % based on fresh feed, consistent
ported Mo catalyst having Mo content of 0.1 to 20 wt %, the with total conversion of the triglycerides and 1 mole of pro
Support being selected from alumina, silica, titania, and com pane formed for each mole of triglyceride converted.
binations thereof, and said Support having a bimodal porous The relatively low HDS, HDN and HDA activity of Cata
structure with pores with a diameter larger than 50 nm that lyst A means that even though all rapeseed oil is converted
constitute at least 2 vol% of the total pore volume, as hydro into hydrocarbons, the conversion of Sulfur and nitrogen spe
deoxygenation (HDO) catalyst for the treatment of feed cies is very low at these conditions. The total aromatics con
stocks combining a fossil hydrocarbon fuel with a renewable 10
tent is unchanged, only a slight conversion of polyaromatics
organic material wherein the content of renewable organic into monoaromatics was observed.
material material is 1 to 35 vol%. This example demonstrates the ability of Catalyst A to
Preferably, the content of renewable organic material in the achieve 100% conversion of triglycerides at typical
feedstock is 10 to 30 vol%, more preferably 15 vol%, for hydrotreating conditions with very little reduction in sulfur,
instance 15 vol% rapeseed oil mixed with 85 vol% fossil 15 nitrogen and aromatics content. Thus, this example proves
LGO; or 25 vol%, for instance 25 vol% FAME (biodiesel) that although the HDO reaction resembles HDS since in both
and 75 vol% LGO. reactions a heteroatom is hydrogenated and taken out of the
The pore volume constituted by pores with a diameter molecule, the HDO catalyst of the invention only containing
above 50 nm (macropores) is preferably at least 10% of the Mo is unexpectedly active in the conversion of triglycerides
total pore volume, more preferably at least 15%. despite being inactive in HDS, HDN, HDA.
EXAMPLE1 EXAMPLE 2

1000 g of amorphous alumina powder is mixed with 850 g Comparative

water for 10 minutes and extruded in /16" trilobe shape. The 25
extrudates are dried and calcined for 2 hours at 600° C. The The feedstock from example 1 (15 vol%. Rapeseed oil/85
carrier is impregnated with a basic solution of ammoniumdi vol% LGO) is processed over Catalyst B (traditional high
molybdate (ADM), dried, and calcined at 400°C. for 2 hours. activity Ni Mo/alumina). The test was carried out at a pres
The amount of ADM is adjusted to produce a catalyst with 3 sure of 30 barg, a temperature of 340°C., a liquid hourly
wt % Mo content on dry weight basis. Below this catalyst is 30
space velocity of 0.95 h", and a H/oil ratio of 260 Nm/m.
termed “Catalyst A’. The properties offeed and liquid product are listed in Table 2.
Catalyst A was characterized by Hg porosimetry. 17% of
the pore Volume was associated with pores having a diameter TABLE 2
of 50 nm or more (macropores).
100 ml of Catalyst A was loaded in an isothermal pilot plant 35 Properties of liquid feed and product in example 2
reactor. A straight-run fossil diesel spiked with TBDS was
used for Sulfiding the catalyst. Property Feedstock Product
As feedstock a 15% by volume rapeseed oil mixed with S.G. (ASTM D4052) O.864 O.845
85% by volume straight run fossil LGO was mixed with S (wt %) (ASTM D4294/ASTM D5453) 1.OS O.O36
hydrogen gas and passed over Catalyst A. The test was carried 40 N (wtppm) (ASTM D4629) 159 30
out at a pressure of 30 barg, a temperature of 320°C., a liquid H (wt %) (ASTM D4808) 12.9 13.7
Mono Aromatics (wt %) (IP391) 13.3 20.7
hourly space velocity of 1.5 h", and a H/oil ratio of 250 Poly Aromatics (wt %) (IP391) 10.3 3.5
Nm/m. The properties offeed and liquid product are listed Simulated Distillation (C.)
in Table 1. (ASTM D2887)
45 5 wt % 234 224
TABLE 1. 10 wt % 253 249
30 wt % 286 284
Properties of liquid feed and product in example 1 SO wt % 3.18 307
70 wt % 358 336
Property Feedstock Product 90 wt % SO8 378
50 95 wt % 6O1 398
S.G. (ASTM D4052) O864 O.845
S (wt %) (ASTM D4294) 1.OS O.98
N (wtppm) (ASTM D4629) 159 121
H (wt %) (ASTM D4808) 12.9 13.3 Similar to Example 1, the distillation curve shows that all
Mono Aromatics (wt %) (IP391) 13.3 13.8 rapeseed oil is converted into hydrocarbons. This is corrobo
Poly Aromatics (wt %) (IP391) 10.3 9.9 55 rated with an observed yield of propane of 0.61 wt % based on
Simulated Distillation (C.) fresh feed, which is within experimental uncertainty of the
(ASTM D2887)
result in Example 1.
5 wt % 234 233 In contrast to Example la much higher conversion of Sulfur
10 wt % 253 255
3O wt % 286 287
and nitrogen containing molecules is observed. Furthermore,
SO wt % 3.18 315 60 the conversion of polyaromatics to monoaromatics is much
70 wt % 358 339 higher than in Example 1. Even when taking the slightly
90 wt % SO8 377
95 wt % 6O1 393
different reaction conditions into account, the degree of HDS,
HDN and Saturation of polyaromatics is as expected higher
when using a high-activity Ni-Mo catalyst than when using
The complete conversion of rapeseed oil at these condi 65 Catalyst A.
tions is evidenced by the removal of all material (triglycer This example thus demonstrates that when using a tradi
ides) boiling above 405°C., as the 95 wt % distillation point tional high-activity promoted hydrotreating catalyst at typical
 US 8,912,375 B2
9 10
hydrotreating conditions the complete conversion of triglyc molar ratio of 350, with 77 wt % amorphous silica-alumina
erides will be associated with a high conversion of sulfur and (high alumina type) and 20 wt % gamma alumina. The result
aromatics. ing mixture was extruded to form /16" extrudates. The extru
The low activity of Catalyst A for these reactions results in dates were dried and calcined at 500° C. for 2 hours in air. The
lower chemical hydrogen consumption as demonstrated by calcined extrudates were impregnated with an aqueous solu
the lower hydrogen content of the product in Example 1 tion containing nickel nitrate and ammonium metatungstate.
compared to the product in Example 2. When using an adia The wet extrudates were dried and calcined at 500° C. for 2
batic reactor, the temperature rise due to the exothermic HDS,
HDN and HDA reactions is significantly lower when using hours in air. The final catalyst contained 6 wt % nickel oxide
Catalyst A prepared in accordance with this invention than 10
(NiO) and 22 wt.% tungsten oxide (WO) (all on dry weight
when using a conventional high-activity promoted basis).
hydrotreating catalyst. As a consequence, the propensity to The hydrodeoxygenated product from Example 1 was col
form coke due to high temperatures and a low local hydrogen lected and analyzed by ASTM D5773 showing a cloud point
partial pressure in the catalyst pellets is lowered. of 7.7°C. and by ASTM D5949 showing a pour point of 2.2°
EXAMPLE 3 15 C. This product was used as feedstock in a new pilot plant test
with Catalyst D. The test was carried out at a pressure of 60
A feedstock consisting of 25 vol % FAME (biodiesel) barg, a temperature of 370° C., a total liquid hourly space
derived from tall oil and 75% light fossil LGO was mixed velocity of 1.0 h", and a H/oil ratio of 300 Nm/m. The
with hydrogen and fed to a isothermal pilot plant reactor other properties of the feed and liquid product are listed in
loaded with a combination of catalyst A and a high-activity Table 4.
conventional Ni-Molalumina hydrotreating catalyst (cata
lyst C). Catalyst A was loaded in the top 20 vol% of the TABLE 4
catalyst bed and Catalyst C was loaded in the bottom 80 vol% Properties of liquid feed and product in example 4
of the catalyst bed. The test was carried out at a pressure of
barg, a temperature of 340°C., a total liquid hourly space 25 Property Feedstock Product
velocity of 1.2 h", and a H/oil ratio of 260 Nm/m. The
properties of feed and liquid product are listed in Table 3. S.G. (ASTM D4052)
S (wt %) (ASTM D4294/ASTMD5453)
O.845
O.98
O.8.204
O.OOO1
N (wtppm) (ASTM D4629) 121 O.1
TABLE 3 H (wt %) (ASTM D4808) 13.3 14.1
30 Mono Aromatics (wt %) (IP391) 13.8 14.8
Properties of liquid feed and product in example 3 Poly Aromatics (wt %) (IP391) 9.9 1.6
Simulated Distillation (C.)
Property Feedstock Product (ASTM D2887)
S.G. (ASTM D4052) O.843 O.816 5 wt % 233 158
S (wt %) (ASTM D5453) 480 3 10 wt % 255 199
N (wtppm) (ASTM D4629) 7 <0.1 35 30 wt % 287 267
H (wt %) (ASTM D4808) 13.0 14.1 SO wt % 315 297
Mono Aromatics (wt %) (IP391) 11.5 13.7 70 wt % 339 318
Poly Aromatics (wt %) (IP391) 4.3 O.S 90 wt % 377 367
Simulated Distillation (C.) 95 wt % 393 381
(ASTM D2887)
40
5 wt %
10 wt %
184
198
178
195
The product was also analyzed by D5773 showing a cloud
3O wt % 224 221 point of 1.5°C. and by ASTM D5949 showing a pour point of
SO wt % 242 238 -6.0°C. This means that the cloud point is lowered by 6.2°C.
70 wt % 26S 261 from feed to product and the pour point is reduced by 8.2°C.
90 wt % 3S4 317 from feed to product.
45
95 wt % 355 3.18
This example demonstrates the ability of hydroisomeriza
tion catalyst D to Substantially lower cloud and pour points
The light fossil LGO that constitutes 75% of the feedstock even when processing a high-sulfur feed, meaning that the
has a final boiling point of approximately 290° C., and when catalyst of the present invention is also active when used for
the product distillation has higher boiling components this is 50 cold flow improvement in an HS atmosphere.
due to the formation of primarily n-Cs, and Small fractions
of n-Co and n-C. The yield of methane was 1.2 wt % based The invention claimed is:
on fresh feed, which is consistent with 1 mole of methane 1. Process for production of a hydrocarbon fuel from
formed per mole of FAME converted at 100% FAME conver renewable organic material of biological origin comprising
sion, taking into account the ca. 10 wt % content of free fatty 55 the steps:
acids and resin acids in the feed.
This example demonstrates the combination of a hydrode (a) forming a feedstock by combining a fossilhydrocarbon
oxygenation step to convert the biological component of the fuel with a renewable organic material wherein the con
feedstock into hydrocarbons over a Mo/alumina catalyst in tent of renewable organic material material is 1 to 35 vol
accordance with the present invention having a low HDS, %; and
HDN and HDA activity and a subsequent step with a highly 60 (b) mixing the feedstock of step (a) with a hydrogen-rich
active Ni-Mo desulfurization catalyst to ensure a low con gas and conducting the combined stream to a hydrode
tent of Sulfur, nitrogen and aromatics in the product. oxygenation stage by contacting said combined stream
with a hydrodeoxygenation catalyst,
EXAMPLE 4 wherein the hydrodeoxygenation catalyst is a Supported
65 unpromoted Mo catalyst having Mo content of 0.1 to 20
Catalyst D was prepared by mixing 3 wt % of a commer wt %, the Support being selected from alumina, silica,
cially available Zeolite beta having a specified SiO: AlO. titania and combinations thereof, and said Support hav
 US 8,912,375 B2
11 12
ing a bimodal porous structure with pores with a diam 9. Process according to claim 1, wherein steps (b), (c) and
eter larger than 50 nm that constitute at least 2 vol% of (d) are carried out in the same hydroprocessing reactor or in
the total pore volume. separate hydroprocessing reactors.
2. Process according to claim 1, wherein the hydrogen-rich 10. Process according to claim 4, wherein the hydrotreat
gas is a hydrogen-recycle gas stream, a hydrogen make-up ing catalyst of step (c) comprises a metal component selected
gas or a combination of both. from Group VIII and/or VI of the Periodic System and being
3. Process according to claim 1, wherein the hydrodeoxy Supported on a carrier containing alumina, silica, titania or
genation catalyst of step (b) is Mo supported on alumina. combinations thereof.
4. Process according to claim 1, further comprising: 11. Process according to claim.5, wherein the hydroisomer
(c) passing the effluent stream from step (b) to a hydrotreat 10
ization treating catalyst of step (d) comprises a metal compo
ing stage by contacting said stream with a hydrotreating
catalyst. nent selected from Group VIII and/or VI of the Periodic
5. Process according to claim 1, further comprising: System and being supported on a carrier containing alumina,
(d) passing the effluent stream from step (b) or (c) to a silica, titania, silica-alumina, ZSM-5, Zeolite beta or combi
hydroisomerization stage by contacting said stream with 15
nations thereof.
a hydroisomerization catalyst. 12. Process according to claim 5, wherein the hydrotreat
6. Process according to claim 1, wherein the renewable ing step (c) and hydroisomerization step (d) are carried out at
organic material is selected from triglycerides, fatty acids, a hydrogen pressure of 1-200 bar and at a temperature of
resin acids, fatty acid esters or combinations thereof. 50-450° C., and at a liquid hourly space velocity of 0.1-10
7. Process according to claim 1, wherein the hydrodeoxy h
genation step (b) is carried out at a hydrogen pressure of 13. A hydrodeoxygenation catalyst in the form of a sup
1-200 bar, at a temperature of 50-350° C., and at a liquid ported unpromoted Mo catalyst having Mo content of 0.1 to
hourly space velocity of 0.1-10 h. 20 wt %, the support being selected from alumina, silica,
8. Process according to claim 1, further comprising sepa titania, and combinations thereof, and said support having a
rating the effluent from any of the steps (b), (c) and (d) into a 25 bimodal porous structure with pores with a diameter larger
liquid effluent stream and a gaseous effluent stream, mixing than 50 nm that constitute at least 2 vol% of the total pore
said liquid effluent stream with a fresh hydrogen-rich gas, Volume, for the treatment of feedstocks combining a fossil
forming a purified hydrogen containing gas stream by remov hydrocarbon fuel with a renewable organic material wherein
ing H2S, NH3. CO, CO2 and light hydrocarbons from said the content of renewable organic material material is 1 to 35
vol%.
gaseous effluent, and recycling said purified hydrogen con
taining gas to any of the steps (b), (c) and (d).