US 2008 OO66374A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2008/00663.74 A1
Herskowitz (43) Pub. Date: Mar. 20, 2008
(54) REACTION SYSTEM FOR PRODUCTION OF Related U.S. Application Data
DESEL FUEL FROM VEGETABLE AND
ANMALS OLS (60) Provisional application No. 60/845,508, filed on Sep.
19, 2006.
Publication Classification
(75) Inventor: Mordechay Herskowitz, Meitar
(IL) (51) Int. Cl.
CIOL L/18 (2006.01)
Correspondence Address: (52) U.S. Cl. ......................................................... 44/308
BUCHANAN, INGERSOLL & ROONEY PC (57) ABSTRACT
POST OFFICE BOX 1404
ALEXANDRIA, VA 22313-1404 A process for producing a fuel composition from vegetable
and/or animal oil comprises feeding the oil to a tubular
reaction unit containing a catalyst comprising an acidic
(73) Assignee: BEN-GURON UNIVERSITY component and a metal component, feeding effluent from the
OF THE NEGEV RESEARCH tubular reaction unit to a vapor-liquid separator, and feeding
& DEVELOPMENT a vapor phase separated from the effluent from the tubular
AUTHORITY, Beer-Sheva (IL) reaction unit to an adiabatic reaction unit comprising the
same catalyst as in the tubular reaction unit comprising an
acidic component and a metal component. The produced
(21) Appl. No.: 11/892,797 fuel composition has acceptable lubricity and comprises a
mixture of C2 to Cs or C to Cs paraffins having a ratio
(22) Filed: Aug. 27, 2007 of iso to normal paraffins of 2 to 8 and less than 5 ppm sulfur.
US 2008/00663.74 A1
REACTION SYSTEM FOR PRODUCTION OF
DESEL FUEL FROM VEGETABLE AND
ANMALS OLS
BACKGROUND
0001 1. Field of Art
0002 Provided is a process and reaction system for the
production of liquid fuels, particularly diesel, jet and naph
tha fuels, from vegetable and/or animal oils.
0003 2. Description of the Related Art
0004 Most combustible liquid fuels used for on road, off
road, stationary engines, and combustion turbines and boil
ers in the world today are derived from crude oil. However,
there are several limitations to using crude oil as a fuel
Source. For example, crude oil is in limited Supply, includes
a high content of aromatics, and contains Sulfur and nitro
gen-containing compounds that can adversely affect the
environment. There is a great desire and need in the industry
to provide combustible liquid fuels that are more environ
mentally friendly, display good engine performance, and
which are available from alternative sources that are abun
dantly renewable.
0005 Vegetable and animal oils are an abundant and
renewable source. The use of vegetable oil in diesel engines
requires significant engine modification, including changing
of piping and injector construction materials, otherwise
engine running times are decreased, maintenance costs are
increased due to higher wear, and the danger of engine
failure is increased. The current conversion of vegetable and
animal oils to combustible liquid fuels typically involves
transesterification of the oils, which are triglycerides of Ca
to C straight-chain carboxylic acids, with a lower alcohol
Such as methanol or ethanol, to form a mixture of methyl or
ethyl esters called “biodiesel. This process is relatively
complex, typical of the chemical industry rather than the
petrochemical industry. Furthermore, the composition of
biodiesel, which is completely different from that of diesel
produced from crude oil, may have adverse effects on engine
performance. Biodiesel exhibits poor low temperature per
formance characteristics and increased nitrogen oxide (NO)
emissions compared to conventional fuels derived from
crude oil.
0006. In the search for alternative and renewable sources,
there is increasing interest in producing liquid fuels from
biological raw materials for use as fuel by themselves or in
mixture with the petroleum-derived fuels in use today. The
patent literature describes methods for producing hydrocar
bon mixtures from biological sources, including vegetable
oils.
0007 United Kingdom Patent Specification 1 524 781
discloses converting ester-containing vegetable oils into one
or more hydrocarbons by pyrolysis at 300 to 700° C. in the
presence of a catalyst which comprises silica-alumina in
admixture with an oxide of a transition metal of Groups IIA,
IIIA, IVA, VA, VIA, VIIA or VIII of the periodic table,
preferably in a fluidized bed, moving bed or fixed bed
tubular reactor at atmospheric pressure.
0008 U.S. Pat. No. 5,705,722 discloses a process for
producing additives for diesel fuels having high cetane
numbers and serving as fuel ignition improvers. In the
process, biomass feedstock selected from (a) tall oil con
taining less than 0.5 wt % ash, less than 25 wt % unsaponi
fiables, up to 50 wt % diterpenic acids and 30 to 60 wt %
unsaturated fatty acids, (b) wood oils from the pulping of
Mar. 20, 2008
hardwood species, (c) animal fats and (d) blends of said tall
oil with plant or vegetable oil containing Substantial
amounts of unsaturated fatty acids or animal fats, is Sub
jected to hydroprocessing by contacting the feedstock with
gaseous hydrogen under hydroprocessing conditions in the
presence of a hydroprocessing catalyst to obtain a product
mixture. This product mixture is then separated and frac
tionated to obtain a hydrocarbon product boiling in the
diesel fuel boiling range, this product being the high cetane
number additive.
0009 U.S. Patent Publication No. 2004/0055209 dis
closes a fuel composition for diesel engines comprising
0.1-99% by weight of a component or a mixture of compo
nents produced from biological raw material originating
from plants and/or animals and/or fish and 0-20% of com
ponents containing oxygen. Both components are mixed
with diesel components based on crude oil and/or fractions
from Fischer-Tropsch process.
O010 U.S. Patent Publication No. 2004/0230085 dis
closes a process for producing a hydrocarbon component of
biological origin comprising at least two steps, the first one
of which is a hydrodeoxygenation step and the second one
is an isomerization step operated using the counter-current
flow principle. A biological raw material containing fatty
acids and/or fatty acid esters serves as the feed Stock.
0011 Fuel properties important for potential diesel appli
cations include: (i) lubricity; (ii) cetane number; (iii) den
sity; (iv) viscosity; (v) lower heating value; (vi) sulfur (vii)
flash point; (viii) cloud point; (ix) Distillation Curve; (x)
carbon residue; (xi) ash; and (xii) Iodine Value. Lubricity
affects the wear of pumps and injection systems. Lubricity
can be defined as the property of a lubricant that causes a
difference in friction under conditions of boundary lubrica
tion when all known factors except the lubricant itself are the
same; thus, the lower the friction, the higher the lubricity.
Cetane number rates the ignition quality of diesel fuels.
Density, normally expressed as specific gravity, is defined as
the ratio of the mass of a volume of the fuel to the mass of
the same volume of water. Viscosity measures the fluid
resistance to flow. Lower heating value is a measure of
available energy in the fuel. Flash point is the lowest
temperature at which a combustible mixture can be formed
above the liquid fuel. Cloud point measures the first appear
ance of wax. Distillation Curve is characterized by the initial
temperature at which the first drop of liquid leaves the
condenser and subsequent temperatures at each 10 vol% of
the liquid. Carbon residue correlates with the amount of
carbonaceous deposits in a combustion chamber. Ash refers
to extraneous solids that reside after combustion. Iodine
Value measures the number of double bonds.
0012. A comparison of properties of biodiesel and EN
Standard EN590: 2005 diesel can be found in Table 1.
TABLE 1.
EN590
Fuel Property Biodiesel Diesel
Density (a) 15° C., kg/m s885 s835
Viscosity (a 40°C., mm/s s4.5 s3.5
Cetane Number s51 s53
90 vol% Distillation, C.
Cloud Point, C.
s355
s-5
s350
s-5
Lower Heating Value, MJ/kg s38 s43
Lower Heating Value, s34 s36
MJ liters
US 2008/00663.74 A1 Mar. 20, 2008

unit is a multi-tubular reaction unit and/or operates in

TABLE 1-continued trickle-bed mode and the adiabatic reaction unit comprises a
EN590
single tube.
Fuel Property Biodiesel Diesel
DETAILED DESCRIPTION
Polyaromatics, wt % O s4
Oxygen, wt % s11 O 0017 High quality liquid fuels, in particular diesel and
Sulfur, mg/kg &10 &10 naphtha fuels, can be obtained from vegetable and/or animal
oils in high yield by a process comprising hydrodeoxygen
ation and hydroisomerization. Triglycerides of fatty acids
0013 The American Society for Testing and Materials contained in the vegetable and/or animal oil are deoxygen
(ASTM) standards for commercial diesel (ASTM D975) and ated to form normal C2 to Cs or C to Cs paraffins, which
biodiesel (ASTM D6751) can be found in Table 2. are hydroisomerized in the same stage to form various
TABLE 2
isoparaffins. Minor cyclization and aromatization to alkyl
cyclohexane and alkylbenzene may also occur. The deoxy
Diesel Biodiesel genation can comprise removal of oxygen in the form of
Fuel Property ASTM D975 ASTM D6751 water and carbon oxides from the triglycerides. Hydrocrack
Lower Heating Value, BTU/gal 129,050 118,170 ing is inhibited, so as to maintain the range of carbon number
Kinematic Viscosity (a) 40° C., 1.3-4.1 4.0-6.0 of hydrocarbons formed in the range of C2 to Cs or C to
cSt Cls.
Specific Gravity (a) 60° C., O.85 O.88 0018 Hydrodeoxygenation of vegetable and/or animal
g/cm oils alone would generate a mixture of long-chain straight
Carbon, wt % 87 77
Hydrogen, wt % 13 12 C. to Cls or C to Cls paraffins. While such long-chain
Oxygen, by dif, wt % O 11 straight C to Cs or C to Cs paraffins would be in the
Sulfur, ppm 500 O paraffin carbon number range of diesel fuels, the fuel prop
Boiling Point, C. 180 to 340 315 to 350 erties of Such long-chain straight C2 to Cs or C4 to Cls
Flash Point, C. 60 to 8O 100 to 170
Cloud Point, C. -15 to 5 -3 to 12 paraffins would be significantly different from those of
Pour Point, C. -35 to -15 -5 to 10 diesel fuels. Therefore, production of diesel fuel requires
Cetane Number 40-5S 48-65 hydroisomerization of the paraffins. Accordingly, the pres
Lubricity (HFRR), Lim 300-600 3OO ently disclosed process for producing a liquid fuel compo
sition comprises providing oil selected from the group
0014. There remains a need for alternative processes for consisting of vegetable oil, animal oil, and mixtures thereof
conversion of vegetable and animal oils to fuels and diesel and hydrodeoxygenating and hydroisomerizing the oil. In
fuel compositions derived from vegetable and animal oils addition to hydrocarbon products within the diesel boiling
having better and more acceptable properties. range, the liquid fuel composition produced by the presently
disclosed process may further comprise 2-10% lighter naph
SUMMARY tha products boiling below 150° C. as well as heavier
distillate products.
00.15 Provided is a process for producing a liquid fuel 0019. The hydrodeoxygenating and hydroisomerizing
composition comprising providing oil selected from the disclosed herein comprises feeding the oil to a tubular
group consisting of vegetable oil, animal oil, and mixtures reaction unit containing a catalyst comprising an acidic
thereof and hydrodeoxygenating and hydroisomerizing the component and a metal component, feeding effluent from the
oil. The hydrodeoxygenating and hydroisomerizing com tubular reaction unit to a vapor-liquid separator, and feeding
prises feeding the oil to a tubular reaction unit containing a a vapor phase separated from the effluent from the tubular
catalyst comprising an acidic component and a metal com reaction unit to an adiabatic reaction unit comprising the
ponent, feeding effluent from the tubular reaction unit to a same catalyst as in the tubular reaction unit comprising an
vapor-liquid separator, and feeding a vapor phase separated acidic component and a metal component. While the effluent
from the effluent from the tubular reaction unit to an from the tubular reaction unit is primarily in a vapor phase,
adiabatic reaction unit comprising the same catalyst as in the liquid separated from the effluent from the tubular reaction
tubular reaction unit comprising an acidic component and a unit can be recycled to the tubular reaction unit. In an
metal component. Liquid separated from the effluent from embodiment, the tubular reaction unit, which is contained
the tubular reaction unit can be recycled to the tubular within a shell, is a multi-tubular reaction unit and/or operates
reaction unit. In an embodiment, the tubular reaction unit is in trickle-bed mode and the adiabatic reaction unit com
a multi-tubular reaction unit and/or operates in trickle-bed prises a single tube.
mode and the adiabatic reaction unit comprises a single tube. 0020. As exothermic hydrodeoxygenation and double
0016. Additionally provided is a reaction system for bond Saturation reactions take place in the tubular reaction
producing a liquid fuel composition comprising a tubular unit, a significant amount of heat of reaction is removed
reaction unit containing a catalyst comprising an acidic from the tube(s) (e.g., 1,000 or even 5,000 tubes) of the
component and a metal component, an adiabatic reaction tubular reaction unit, for example, by coolant contained in a
unit containing the same catalyst as in the tubular reaction shell jacketing the tube(s) for optimal temperature control.
unit comprising an acidic component and a metal compo The vapor-liquid separator disposed downstream of the
nent, and a vapor-liquid separator disposed between the tubular reaction unit functions as a heat exchanger and sets
tubular reaction unit and the adiabatic reaction unit. The the temperature of the vapor phase exiting the vapor-liquid
adiabatic reaction unit can be located downstream of the separator, which is to be fed to the reaction unit following
tubular reaction unit. In an embodiment, the tubular reaction the vapor-liquid separator. In an embodiment, the vapor
US 2008/00663.74 A1
phase leaves the vapor-liquid separator at a temperature of
about 330 to 400° C. As mild, vapor-phase hydroisomeriza
tion and similar reactions take place in the reaction unit
following vapor-liquid separation, the reaction unit is adia
batic, and thus, in addition to setting the temperature of the
vapor phase exiting the vapor-liquid separator, the vapor
liquid separator also sets the temperature of the reaction unit
following the vapor-liquid separator and allows for optimi
zation of the process. Use of both tubular and adiabatic
reaction units allows for optimization of the hydrodeoxy
genating and hydroisomerizing and improved performance
and stability of the catalyst. The tubular reaction unit,
vapor-liquid separator, and adiabatic reaction unit may be
contained within one or more reaction vessels.
0021. In an embodiment, catalysts for the presently dis
closed process are dual-functional catalysts comprising a
metal component and an acidic component. In an embodi
ment, metal components are platinum or palladium. In an
embodiment, the metal component is platinum. The acidic
component can comprise an acidic function in a porous solid
Support. In an embodiment, acidic components include, for
example, amorphous silica aluminas, fluorided alumina,
ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38,
ZSM-48, ZSM-57, SSZ-32, ferrierite, SAPO-11, SAPO-31,
SAPO-41, MAPO-11, MAPO-31, Y. Zeolite, L. Zeolite and
Beta Zeolite. In an embodiment, the catalyst is Pt/SAPO-11,
specifically 0.5-1 wt % Pt/SAPO-11, more specifically 1 wt
% Pt/SAPO-11.
0022. The type and content of metal, acid strength, type
and concentration of acid sites, Solid porosity and pore size
affect the type and quality of the diesel fuel produced. U.S.
Pat. Nos. 5,082,986, 5,135,638, 5,246,566, 5,282,958, and
5,723,716, the entire contents of which are hereby incorpo
rated by reference, disclose representative process condi
tions using said catalysts for isomerization of different
hydrocarbon feedstock. Further, typical processes and cata
lysts for dewaxing and hydroisomerization are described, for
example, in U.S. Pat. No. 6,702.937, the entire content of
which is hereby incorporated by reference, and the refer
ences cited therein.
0023 The process is carried out at relatively mild con
ditions, for example, the tubular reaction unit is operated at
conditions comprising a liquid hourly space Velocity
(LHSV) in the range of 0.5-5 h", for example, 0.6-3 h",
0.7-1.2 h", or 1-2.5 h", at a temperature varying between
300 and 450° C., for example, between 320 and 400° C., at
a pressure varying between 10 and 60 atm, for example,
20-40 atm, and a H/oil ratio of about 300-1200 NL/L, for
example, 500-1000 NL/L. More severe conditions result in
liquid fuel compositions with poorer lubricity, while more
moderate to mild conditions result in liquid fuel composi
tions with better lubricity.
0024 Lubricity is especially important with regard to
modern diesel fuels, as modern engines have very high
injection pressures in excess of 24,000 pounds per square
inch. Good lubricity is necessary to prevent risk of cata
strophic engine failure. In general, an acceptable lubricity
refers to a lubricity that would allow modern engines to
operate more efficiently. In an embodiment, the diesel fuel
has a maximum high-frequency reciprocating rig (HRFF)
lubricity of 400 um (according to International Organization
for Standardization (ISO) standard 12156/1), in accordance
with the recommendation of the World Wide Fuel Charter,
Category 4. In an embodiment, the lubricity is less than 300
Mar. 20, 2008
um according to ISO 12156/1, for example, the lubricity is
less than 200 um according to ISO 12156/1.
0025. Any vegetable and/or animal oil can be used in the
presently disclosed process. For example, Suitable vegetable
oils include Soybean oil, palm oil, corn oil, Sunflower oil,
oils from desertic plants such as, for example, jatropha oil
and balanites oil, rapeseed oil, colza oil, canola oil, tall oil,
safflower oil, hempseed oil, olive oil, linseed oil, mustard
oil, peanut oil, castor oil, coconut oil, and mixtures thereof.
In an embodiment, vegetable oils include Soybean oil, palm
oil, corn oil, Sunflower oil, jatropha oil, balanites oil, for
example, from Balanites aegyptiaca, and mixtures thereof.
The vegetable oil may be genetically modified oil, produced
from transgenic crops. The vegetable oil may be crude
vegetable oil or refined or edible vegetable oil. If crude
vegetable oil is used, the vegetable oil can be pretreated, for
example, to separate or extract impurities from the crude
vegetable oil. Suitable animal oils include, for example, lard
oil, tallow oil, train oil, fish oil, and mixtures thereof.
Further, the vegetable and/or animal oil may be new oil,
used oil, waste oil, or mixtures thereof.
0026. The oil, or mixture of oils, used in the presently
disclosed process can contain a high content of fatty acids
(e.g., greater than or equal to 70 wt % fatty acids). Addi
tionally, compositions derived from vegetable and/or animal
oil that contains a high content of fatty acids can be used in
the presently disclosed process. The phrase “compositions
derived from vegetable and/or animal oil” refers to compo
sitions which originate from or are the byproduct of pro
cessing vegetable and/or animal oil (e.g., vapor overhead
stream from distilling vegetable and/or animal oil, residual
non-vaporizable remaining portion, etc.). Thus, palm oil
distillate containing greater than 70 wt % fatty acids can be
used in the presently disclosed process.
0027. The diesel fuel composition produced by the pres
ently disclosed methods comprises a mixture of C to Cs
or C to Cs paraffins with a ratio of iso to normal paraffins
from 0.5 to 8, for example, from 2 to 8, from 2 to 6, from
2 to 4, from 1 to 4, or from 4 to 7; less than 5 ppm sulfur,
for example, less than 1 ppm Sulfur, and acceptable lubricity.
Specifically, the diesel fuel composition can have a lubricity
of less than 400 um, for example, less than 300 um or less
than 200 um, according to ISO 12156/1.
0028. Additionally, the diesel fuel composition can com
prise less than or equal to 0.6 wt %, for example, 0.1-0.6 wt
%, of one or more oxygenated compounds, which, without
wishing to be bound by any theory, are believed to contrib
ute to the acceptable lubricity of the diesel fuel composition.
In an embodiment, the one or more oxygenated compounds
comprise acid, for example, one or more fatty acids. In an
embodiment, the one or more oxygenated compounds (e.g.,
acid), is present in an amount of less than or equal to 0.4 wt
%, for example, 0.1-0.4 wt %. As used herein, the phrase
"fatty acids’ refers to long chain Saturated and/or unsatur
ated organic acids having at least 8 carbon atoms, for
example, 12 to 18 or 14 to 18 carbon atoms. Without wishing
to be bound by any theory, it is believed that the low content
of one or more oxygenated compounds, for example, one or
more fatty acids, in the diesel fuel composition may con
tribute to the acceptable lubricity of a diesel fuel composi
tion; such oxygenated compounds, present in the vegetable
and/or animal oil feedstock, may Survive the non-severe
hydrodeoxygenation/hydroisomerization conditions
employed in the presently disclosed process. The diesel fuel
US 2008/00663.74 A1 Mar. 20, 2008

composition may comprise alkyl cyclohexane, for example,

less than 10 wt %, and/or alkyl benzene, for example, less TABLE 3-continued
than 15 wt %.
0029. The characteristics of the diesel fuel composition, Comparative Comparative
Example 1 Example 1
and naphtha, produced by the presently disclosed methods Stage 1 Stage 2
may vary depending on the vegetable and/or animal oil
starting product, process conditions, and catalyst used. In an LHSV, hir' 1.O 3.0
Pressure, atm 40 50
embodiment, selection of vegetable and/or animal oil start Hfoil ratio, NLL 1200 500
ing product, process conditions, and catalyst allows for high Distillation Temperature
yield of high quality diesel fuel composition, with preferred ASTM D86
properties, and minimized production of lighter components BP 194.1° C. 150° C.
including, for example, naphtha, carbon oxides and C to Ca O% 292.8° C. 191.1° C.
hydrocarbons. The paraffinic diesel fuel compositions pro SO% 3O3.6° C. 295.4° C.
duced by the presently disclosed methods provide superior 90% 369.0° C. 356.0° C.
fuel properties, especially for low temperature performance Up to 250° C.
Up to 350° C.
2.0%
86.5%
18.1%
89.4%
(e.g., density, Viscosity, cetane number, lower heating value, Cold Filter Plugging Point (CFPP) 17o C. &-20° C.
cloud point, and CFPP), to biodiesel, a mixture of methyl or P309
ethyl esters. In contrast to the products of the process Lubricity (HFRR) 352 m 502 m
disclosed in U.S. Patent Publication No. 2004/0230085, SO 12156.1
Cloud Point 17o C. &-20° C.
disclosed herein are method for producing diesel fuel com ASTM D2500
positions with acceptable lubricities produced from Veg Kinematic Viscosity (a) 40° C. S.25 cSt 2.97 cSt
etable and/or animal oil. More specifically, fuel properties, ASTM D445
Such as, for example, lubricity, may be controlled through Specific Gravity (a) 15° C. 0.806 g/cm 0.788 g/cm
ASTM D1298
variation of process conditions and/or catalyst(s). In general, Composition, wt %
with regards to the distillation curve of the diesel fuel
composition produced by the presently disclosed methods, Linear paraffins S1.O 14.O
the initial boiling point (IBP) is in the range of 160°C.-240° Branched paraffins 28.0 76.8
Alkyl cyclohexane 9.2 5.5
C. and the 90 vol% distillation temperature is in the range Alkyl benzene 2.2 O6
of 300°C.-360° C. The produced naphtha is highly pure and Olefins 2.7 O.3
particularly Suitable for use as a solvent and/or chemical Acids O.2 Not Detected
feedstock, e.g., a cracking Stock. Others 6.7 2.8
Degree of Saturation O6 O.8
ASTM D1959-97
EXAMPLES
*Detection limit of 0.1 wt %
0030 The following examples are intended to be non
limiting and merely illustrative. 0032 The diesel product from Stage 2 exhibited a poorer
Comparative Example 1 lubricity (502 um) as compared to that of the organic phase
from Stage 1 (352 um). Without wishing to be bound by any
Production of Diesel from Soybean Oil Based on theory, it is believed that the increase in ratio of branched to
U.S. Patent Publication No. 2004/0230085
linear paraffins in the diesel product from Stage 2, as
0031 Refined soybean oil was fed to a fixed-bed reactor compared to the organic phase from Stage 1, resulted in a
packed with a granulated Ni Mo catalyst operated at an change of fuel properties.
LHSV of 1.0 h", 375° C., 40 atm, and an H/oil ratio of
1200 NL/L (Stage 1). The total liquid product was separated Comparative Example 2
into two phases, water and an organic phase. The organic
phase was fed to a fixed-bed reactor packed with a granu Production of Diesel from Soybean Oil by a Two
lated 1 wt % Pt/SAPO-11 catalyst operated at an LHSV of
3.0 h", 380° C., 50 atm, and an H/oil ratio of 500 NL/L Stage Process
(Stage 2). The organic phase from Stage 1 and the diesel
product from Stage 2 were analyzed according to ASTM 0033 Refined soybean oil was fed to a fixed-bed reactor
methods and their compositions were measured by GC-MS packed with a granulated 1 wt % Pt/SAPO-11 catalyst
and confirmed by NMR. The results can be found in Table operated at an LHSV of 1.0 h", 380° C., 20 atm, and an
3. H/oil ratio of 1200 NL/L (Stage 1). The total liquid product
was separated into two phases, water and diesel product. The
TABLE 3
diesel product from Stage 1 was fed to a fixed-bed reactor
Comparative Comparative packed with a granulated 1 wt % Pt/SAPO-11 catalyst
Example 1 Example 1
Stage 1 Stage 2 operated at an LHSV of 4.5 h", 360° C., 30 atm, and an
Oil Soybean Soybean
H/oil ratio of 1200 NL/L (Stage 2). The diesel product from
Temperature 375 C. 380° C. Stage 1 and the diesel product from Stage 2 were analyzed
Catalyst Granulated Granulated according to ASTM methods and their compositions were
Ni–Mo 1 wt % Pt
SAPO-11 measured by GC-MS and confirmed by NMR. The results
can be found in Table 4.
US 2008/00663.74 A1 Mar. 20, 2008

reactor simulations using soybean oil. In the kinetic studies,

TABLE 4 concentrations of the Soybean oil, acids, paraffins, olefins,
Comparative Comparative
cyclohexanes, aromatics and light compounds were mea
Example 2 Example 2 Sured as a function of residence time and temperature.
Stage 1 Stage 2 Vapor-liquid equilibrium was provided by the reactor simu
lations. For a residence time of 15 to 25 minutes, the
Oil Soybean Soybean Soybean oil was nearly completely converted. The acid
Temperature 380° C. 360° C.
Catalyst Granulated Granulated content in the product(s) peaked at about 10 to 15 minutes,
1 wt % Pt 1 wt % Pt and then decreased with additional residence time. Again,
SAPO-11 SAPO-11 diesel fuel compositions produced in accordance with the
LHSV, hir 1.O 4.5 presently claimed methods can comprise less than or equal
Pressure, atm 2O 30
Hafoil ratio, NLL 1200 1200 to 0.6 wt % of one or more oxygenated compounds (e.g.,
Distillation Temperature acids). In part due to the operating pressure, conversion of
ASTM D86 the soybean oil (e.g., for a residence time of 15 to 25
BP 1813 C. 189.7 C.
minutes) resulted in vapor phase products with only very
O% 263.9° C. 263.5° C. Small amounts of liquid products, which contain heavy
SO% 292.5° C. 292.6° C. compounds (e.g., Co. hydrocarbons).
90% 360.3° C. 353.7 C. 0037 Accordingly, refined soybean oil was fed to a single
Up to 250° C. 5.6% 5.4% (electrically heated) wall-cooled reactor tube, packed with a
Up to 350° C. 88.9% 89.7%
Cold Filter Plugging Point (CFPP) -14°C. -17 C. granulated 1 wt % Pt/SAPO-11 catalyst, and operated in
P309 trickle-bed mode at an LHSV of 3.5 h", 382° C., 30 atm,
Lubricity (HFRR)
SO 12156.1
306 Lim 437 Im and an H/oil ratio of 550 NL/L. The effluent of the single
Cloud Point -12°C. -14° C.
wall-cooled reactor tube flowed through a gas-liquid sepa
ASTM D2500 rator maintained at 30 atm and 3.73° C., in which a very
Kinematic Viscosity (a) 40° C. 3.82 cSt 3.60 C?t small amount of liquid (i.e., 0.2 wt % of the refined soybean
ASTM D445 oil fed to the single wall-cooled reactor tube) was separated
Specific Gravity (a) 15° C. 0.789 g/cm 0.794 g/cm from a vapor phase. The vapor phase from the separator
ASTM D1298
Composition, wt % flowed upward to a single tube, adiabatic, fixed-bed reaction
unit packed with a granulated 1 wt % Pt/SAPO-11 catalyst
Linear paraffins
Branched paraffins
26.8
52.3
23.6
58.4
operated at an LHSV of 1.4 h", 373-375° C., 30 atm, and
Alkyl cyclohexane 4.9 8.1 an H/oil ratio of 550 NL/L. The diesel product from the
Alkyl benzene 7.7 2.9 adiabatic reaction unit was analyzed according to ASTM
Olefins 2.9 2.9 methods and its composition was measured by GC-MS. The
Acids 0.4 Not Detected results can be found in Table 5.
Others S.O 4.1
Degree of Saturation 0.4 O.S
ASTM D1959-97 TABLE 5

*Detection limit of 0.1 wt % Example 3

0034. The diesel product from Stage 1 exhibited accept Distillation Temperature
ASTM D86
able properties, including a lubricity of 306 Lum. As the
composition of the diesel product from Stage 2 did not IBP 143.8° C.
significantly differ from the diesel product from Stage 1, the 10% 268.5° C.
properties of the diesel product from Stage 2 are similar to SO% 293.6° C.
those of the diesel product from Stage 1. However, the diesel 90% 355o C.
product from Stage 2 exhibited a poorer lubricity (437 um) Up to 250° C. S.1%
as compared to that of the diesel product from Stage 1 (306 Up to 350° C. 89.7%
um), similar to the diesel production from Stage 2 of Cold Filter Plugging Point (CFPP) -20° C.
IP 309
Comparative Example 1. Without wishing to be bound by Lubricity (HFRR) 346 m
any theory, it is believed that water may act as an inhibitor ISO 12156.1
to isomerization, which requires higher catalyst activity, and Flash Point 59 C.
the removal of water between Stage 1 and Stage 2 in Kinematic Viscosity (a) 40° C. 3.76 cSt
Comparative Example 1 and Comparative Example 2 may ASTM D445
also remove acid, thereby affecting final product lubricity. Specific Gravity (a) 15° C. 0.802 g/cm
ASTM D1298
0035. Adding 0.1 wt % of oleic acid to the diesel product Composition, wt %
of Stage 2 improved its lubricity from 437 um to 270 um.
Thus, as noted above, without wishing to be bound by any Linear paraffins 2O
theory, it is believed that the low content of one or more Branched paraffins
Alkyl cyclohexane
64
7
oxygenated compounds, such as one or more fatty acids, in Alkyl benzene 7
the product of the process may contribute to the acceptable Olefins 2
lubricity of the diesel product. Acids O.2
Example 3
Production of Diesel from Soybean Oil in a Two 0038. The diesel product according to Example 3 exhib
Unit Process ited acceptable properties, including a lubricity of 346 Lum.
0036. The reactor setup and the operating conditions of 0039. The temperature of the adiabatic reaction unit
Example 3 were based on the results of kinetic studies and following the vapor-liquid separator is set by the tempera
US 2008/00663.74 A1
ture of the vapor-liquid separator. Heat loss can cause a
temperature drop in the vapor phase products from the
tubular reaction unit. Assuming that heat loss is avoided, if
the temperature of the vapor-liquid separator is low (i.e.,
lower than the temperature of the vapor phase products from
the tubular reaction unit), the vapor phase products may
undesirably condense to liquid prior to hydroisomerization
in the adiabatic reaction unit. Therefore, the temperature of
the vapor-liquid separator can be set Such that the tempera
ture of the vapor-liquid separator is close to the temperature
of the tubular reaction unit, and more specifically, the
temperature of the vapor phase products from the tubular
reaction unit. Most of the heat of the hydrodeoxygenation
and hydroisomerization reaction is generated in the tubular
reaction unit, which can be a wall-cooled reactor. Accord
ingly, the reaction unit downstream of the vapor-liquid
separator can be run adiabatically. The vapor-liquid separa
tor, which can provide different conditions in the down
stream adiabatic reaction unit than in the upstream tubular
reaction unit, can also ensure that the downstream adiabatic
reaction unit is run in vapor phase.
0040. For example, the temperature of the adiabatic reac
tion unit following the vapor-liquid separator can be set in
the range of about 350 to 400° C. or about 360 to 385° C.
In particular, the temperature of the vapor-liquid separator in
Example 3 was maintained at 373° C. and the temperature
of the adiabatic reaction in Example 3 was operated at 373°
C., to minimize condensation of vapor phase products to
liquid prior to hydroisomerization in the adiabatic reaction
unit. Thus, the vapor-liquid separator can be used to set the
temperature of the adiabatic reaction unit following the
vapor-liquid separator.
0041 As noted above, the effluent from the single wall
cooled reactor tube is primarily in a vapor phase (e.g., vapor
phase can comprise about 95 to 99.9 wt % of the effluent).
The liquid separated from the vapor phase in the vapor
liquid separator can contain as much as 40 wt % acids. The
catalyst contained in the reaction units is sensitive to coking
and deactivation as a result of contact with heavy com
pounds (e.g., acids) in the liquid products. Thus, liquid
products can negative affect selectivity of desired products
and Stability of the catalyst. Accordingly, separation of
liquid from the vapor phase in the vapor-liquid separator
(i.e., the vapor phase to be fed to the adiabatic reaction unit),
protects catalyst in the adiabatic reaction unit and prevents
deactivation thereof. Consequently, while catalyst in the
upstream tubular reaction unit can be prone to deactivation
as a result of contact with heavy compounds (e.g., acids) in
the liquid products, separating liquid product in the vapor
liquid separator prior to the downstream adiabatic reaction
unit can avoid the need to regenerate catalyst in the down
stream adiabatic reaction unit. Thus, use of both tubular
(e.g., single wall-cooled reactor tube or multi-tubular) and
adiabatic reaction units, and a vapor-liquid separator dis
posed therebetween, allows for improved performance and
stability of the catalyst, especially the catalyst contained
within the adiabatic reaction unit. In particular, the life of the
catalyst contained within the adiabatic reaction unit can be
extended as a result of using a vapor-liquid separator dis
posed between the tubular and adiabatic reaction units.
0042. While various embodiments have been described,
it is to be understood that variations and modifications can
be resorted to as will be apparent to those skilled in the art.
Mar. 20, 2008
Such variations and modifications are to be considered
within the purview and scope of the claims appended hereto.
What is claimed is:
1. A process for producing a liquid fuel composition
comprising:
providing oil selected from the group consisting of veg
etable oil, animal oil, and mixtures thereof; and hydro
deoxygenating and hydroisomerizing the oil, wherein
the hydrodeoxygenating and hydroisomerizing com
prises:
feeding the oil to a tubular reaction unit containing a
catalyst comprising an acidic component and a metal
component;
feeding effluent from the tubular reaction unit to a
vapor-liquid separator, and
feeding a vapor phase separated from the effluent from
the tubular reaction unit to an adiabatic reaction unit
comprising the same catalyst as in the tubular reac
tion unit comprising an acidic component and a
metal component.
2. The process of claim 1, wherein the tubular reaction
unit comprises a multi-tubular reaction unit.
3. The process of claim 1, wherein hydrodeoxygenating
occurs in the tubular reaction unit and hydroisomerizing
occurs in the adiabatic reaction unit.
4. The process of claim 1, further comprising recycling
liquid separated from the effluent from the tubular reaction
unit to the tubular reaction unit.
5. The process of claim 1, wherein the tubular reaction
unit operates in trickle-bed mode.
6. The process of claim 1, wherein the adiabatic reaction
unit comprises a single tube.
7. The process of claim 1, comprising operating the
tubular reaction unit at conditions comprising:
a liquid hourly space velocity of 0.5 to 5 hr';
a temperature of 300 to 450° C.:
a pressure of 10 to 60 atm; and
a H/oil ratio of 300 to 1200 NL/L.
8. The process of claim 1, wherein the vapor phase has a
temperature of about 330 to 400° C.
9. The process of claim 1, comprising operating the
adiabatic reaction unit at a temperature of about 350 to 400°
C.
10. The process of claim 1, wherein the metal component
is selected from the group consisting of platinum and
palladium and the acidic component is selected from the
group consisting of amorphous silica alumina, fluorided
alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35,
ZSM-38, ZSM-48, ZSM-57, SSZ-32, ferrierite, SAPO-11,
SAPO-31, SAPO-41, MAPO-11, MAPO-31, Y. Zeolite, L
Zeolite, and beta Zeolite.
11. The process of claim 9, wherein the catalyst is
Pt/SAPO-11.
12. The process of claim 10, wherein the catalyst is 0.5-1
wt % Pt/SAPO-11.
13. The process of claim 1, wherein the vegetable oil is
selected from the group consisting of Soybean oil, palm oil,
corn oil, Sunflower oil, jatropha oil, balanites oil, rapeseed
oil, colza oil, canola oil, tall oil, safflower oil, hempseed oil,
olive oil, linseed oil, mustard oil, peanut oil, castor oil,
coconut oil, and mixtures thereof.
14. The process of claim 1, wherein the animal oil is
selected from the group consisting of lard oil, tallow oil,
train oil, fish oil, and mixtures thereof.
US 2008/00663.74 A1
15. A reaction system for producing a liquid fuel compo
sition comprising:
a tubular reaction unit containing a catalyst comprising an
acidic component and a metal component;
an adiabatic reaction unit comprising the same catalyst as
in the tubular reaction unit comprising an acidic com
ponent and a metal component; and
a vapor-liquid separator disposed between the tubular
reaction unit and the adiabatic reaction unit.
16. The reaction system of claim 15, wherein the tubular
reaction unit comprises a multi-tubular reaction unit.
17. The reaction system of claim 15, wherein the adiabatic
reaction unit comprises a single tube.
18. The reaction system of claim 15, wherein the tubular
reaction unit operates in trickle-bed mode.
Mar. 20, 2008
19. The reaction system of claim 15, wherein the adiabatic
reaction unit is located downstream of the tubular reaction
unit.
20. The reaction system of claim 15, wherein the metal
component is selected from the group consisting of platinum
and palladium and the acidic component is selected from the
group consisting of amorphous silica alumina, fluorided
alumina, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35,
ZSM-38, ZSM-48, ZSM-57, SSZ-32, ferrierite, SAPO-11,
SAPO-31, SAPO-41, MAPO-11, MAPO-31, Y. Zeolite, L
Zeolite, and beta Zeolite.