US 20090163744A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2009/0163744 A1
Abhari et al.
(54)

(43) Pub. Date:

HYDRODEOXYGENATION PROCESS

(76) Inventors:

.
.
Ramln
Abharl,. Blxby,
OK (U S);

Jun. 25, 2009

Publication Classi?cation

( 51)

Int. Cl.

(52)

US. Cl. ....................................... .. 568/876; 585/733

Peter Havlik, Tulsa, OK (US)

C07C 27/02

(200601)

Correspondence Address:
Hall, Estill, Hardwick, Gable, Golden &

(57)

Nelson, RC,
100 North Broadway, Chase Tower, Suite 2900
Oklahoma City, OK 73102 (US)

A process for producing a hydrocarbon from biomass. A feed

stream having free fatty acids, fatty acid esters or combina
tions thereof is provided. The feed stream is heated in the
presence of a ?rst catalyst to produce a partially hydrodeoxy

(21) Appl, No;

11/961,501

ABSTRACT

genated stream. The partially hydrodeoxygenated stream is

heated in the presence of a second catalyst to produce an

(22) Filed;

Dec, 20, 2007

effluent stream containing the hydrocarbon.

Patent Application Publication

Jun. 25, 2009 Sheet 1 0f 3

US 2009/0163744 A1

Patent Application Publication

Jun. 25, 2009 Sheet 2 0f 3

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Patent Application Publication

Jun. 25, 2009 Sheet 3 0f 3

US 2009/0163744 A1

US 2009/0163744 A1

Jun. 25, 2009

HYDRODEOXYGENATION PROCESS

at high temperature and reduce catalyst activity. HoWever the

level of dilution reported for good results is betWeen 3% and

STATEMENT REGARDING FEDERALLY

SPONSORED RESEARCH OR DEVELOPMENT

20%. This level of feed dilution translates to a signi?cant

increase in reactor siZe and separation/recycle costs.
[0012] Use of pre-hydrogenation to saturate the double
bonds in the triglyceride is described in other prior art. HoW
ever, this pre-hydrogenation describes the Well-known veg
etable oil hydrogenation process Which does not remove any
oxygen. As such, the hydrogenolysis load on the main HDO

[0001] Not applicable.

CROSS-REFERENCE TO RELATED
APPLICATIONS

[0002] Not applicable.

BACKGROUND OF THE INVENTION

[0003]
[0004]

1. Field of the Invention

The present invention relates generally to a process
Which removes oxygen from biomass, and more particularly,
not by Way of limitation, to an improved hydrodeoxygenation
process.

[0005]

2. Brief Description of the Related Art

[0006]

Biomass is a reneWable alternative to fossil raW

catalyst is not affected by such pre-hydrogenation.

[0013] To this end, although processes of the existing art
utiliZe biomass to produce biofuels, further improvements are
desirable to increase HDO ef?ciency, reduce Water partial
pressure in the reactor, achieve a loW capital/loW operating
cost method of removing heat from the ?xed-bed reactor
system, or address the problems With high acid feeds (char

acteristic of fatty acid containing biomass), Which impacts

materials in production of liquid fuels and chemicals.

Increase of biofuels production is part of the governments
strategy to improve energy security and reduce green house

preheater/reactor metallurgy and catalyst attrition. It is to

gas emissions. HoWever, most biomass has high oxygen con

BRIEF DESCRIPTION OF THE DRAWINGS

tent Which loWers fuel quality and heat value. Upgrading

biomass or biomass intermediates into high quality hydrocar
bon fuels thus requires removal of oxygen. The biomass
oxygen may be in the form of an ester, carboxylic acid or

hydroxyl groups.
[0007] Removal of oxygen by catalytic reaction With
hydrogen is referred to as hydrodeoxygenation (HDO). This
reaction may be conducted With conventional ?xed-bed
bimetallic hydrotreating catalysts such as sul?ded nickel

molybdenum (NiMo) or cobalt-molybdenum (CoMo) Which

are commonly used in re?neries.
[0008] Unre?ned vegetable oils and animal fats have sev

eral hundred ppm phosphorus in the form of pho spholipids. In

such a process that the present invention is directed.

[0014]

FIG. 1 is a schematic diagram of an operation of a

hydrodeoxygenation process according to the present inven

tion.

[0015] FIG. 2 is a schematic diagram shoWing an altema

tive embodiment of a hydrodeoxygenation process according
to the present invention.

[0016]

FIG. 3 is a gas chromatogram of Run 1 shoWn in

Table III.

[0017]

FIG. 4 is a gas chromatogram of Run 2 shoWn in

Table III.

addition, animal fats may contain up to a thousand ppm metal

chloride salts. The salts are soluble in the fat/ grease feed, but
come out of solution during the HDO reaction and plug the

SUMMARY OF THE INVENTION

catalyst bed. The metals/ salts can also deactivate the catalyst
by reducing available pore surface. In the presence of free
fatty acids, metal chlorides may form soluble soaps (e.g.

[0018] Vegetable oils, animal fats, and greases are glycer

ides (di- and tri-esters) With varying concentrations of free

calcium stearate). In such form, metals are dif?cult to remove

fatty acids (carboxylic acids).

Several prior art processes for producing fuels from

[0019] The ideal triglyceride HDO conversion is shoWn in

Equation (1). More typically, the HDO reaction is accompa
nied by the DCO reaction shoWn in Equation (2). Since DCO

starting materials such as plants and animals are knoWn.

involves loss of a carbon atom While HDO does not, the ideal

using conventional cleanup technologies such as Water Wash

mg.

[0009]

Conversion of vegetable oils to n-paraf?ns has been reported

HDO reaction is preferred for high hydrocarbon yields. Fur

in the prior art. Some prior art has shoWn that the process may
be applied to other forms of biomass such as tall oil fatty

thermore, DCO generates CO2 and CO Which need to be

removed from the recycle hydrogen, thus adding to the co st of

acids, animal fats, and restaurant greases. HydroisomeriZa

tion of the bio-derived n-paraf?ns to isopara?inic diesel has
been taught in the prior art.

the HDO process.

[0010] Other prior art describes use of feed treatment

upstream of an HDO reactor. Overall cleanup ef?ciency of
75% is reported. HoWever no attempt is made to improve the

hydrocarbon yields by increasing HDO ef?ciency. In fact the

CO+CO2 yields reported are as high as 15% (Which is near

[0020] By conducting the HDO conversion in tWo selective

steps, the ideal Equation (1) conversion for the triglyceride is
accomplished. The tWo selective HDO steps involve: l)
cracking of the triglyceride into a fatty alcohol and a diester

(Equation (3)), and 2) hydrodeoxygenating the fatty alcohol

and the diester to paraf?ns (Equations (5) and (6)). (Equation

theoretical maximum decarboxylation (DCO), suggesting

(3)+Equation (5)+Equation (6):Equation (1)). The ?rst step

very loW HDO e?iciency).

uses a loW activity catalyst such as Mo, the second step

[0011] Still other prior art teaches use of feed dilution to

achieve better catalyst life. Solvent dilution is used to loWer
average bed temperatures for the exothermic HDO reaction,
Which in turn reduces the heavy side products that are formed

requires use of higher activity catalysts such as NiMo. The

process uses tWo different types of catalysts to achieve tWo
selective HDO reactions. The ?rst step HDO reaction also

converts the free fatty acid according to Equation (4).

US 2009/0163744 A1

Jun. 25, 2009

Equations:

periodic table, as fully reduced metal or metal sul?de. Since

the ?rst stage HDO reactor 108 acts as a guard reactor for a

[0021]

second stage HDO reactor, provisions for mitigating fouling

are made by using larger-size, high void catalysts. One
example of a catalyst that may be used in the ?rst stage HDO
reactor 108 is TK-709 commercially available from Haldor
Topsoe. The reaction Which occurs in the ?rst stage HDO

reactor 108 converts the fatty acids to para?in (Equation (4)),

While cracking the triglycerides into fatty alcohols and
smaller esters (Equation (3)).
[0023] The e?iuent 109 of the ?rst stage HDO reactor 108
is cooled through a feed-effluent heat exchanger 11011. A

cooled stream 111 contains hydrocarbons, fatty alcohols, and

esters in liquid phase, and hydrogen and Water vapor in gas
phase. Additional Water is introduced to Wash the salt deposits
that are formed upon condensation of Water. The tWo phase
cooled stream 111 is cooled further in air cooler 11019 to

condense all Water. Water, organic liquid, and hydrogen-rich

vapor are separated in a three-phase separator drum 112.

[0024] With the fatty acids converted in the ?rst stage HDO
reactor 108, the metals not trapped in the catalyst are expected

CH2

H2O

CH2_OCOC17H33
(1,3- and 1,2-diesters)

(4)
>

C18H38

ZHZO

(5)

to be removed With drum 112 Water stream 1130. A hydrogen

rich vapor phase 11311 from drum 112 is recycled to the HDO
reactors. A partially hydrodeoxygenated liquid 11319 is com
bined With recycled hydrogen 135. A combined stream 114 is
heated in the heat exchanger 113a before entering a second
stage HDO reactor 116 at about 550 F. Since the fatty acids
Were converted in reactor 108, the heat exchanger 11a and the
second stage HDO reactor 116 need not be designed for acid
service. The remaining oxygen atoms in the fatty alcohol and
diester intermediate are removed via hydrogenolysis over a

CH2

10H2

>

zclgn38

bimetallic catalyst, such as sul?ded NiMo on alumina in the

second stage HDO reactor 116 (Equations (5) and (6)). Other
CH2OCOC17H33

catalysts suitable for use in reactor 116 include sul?ded

CoMo and NiMo on supports such as alumina, aluminum

(1,3- and 1,2-diesters)

C3H8

4 H20

phosphate, silica, or combinations thereof.

[0025] Ef?uent 117 is cooled in the heat exchanger 105. A
cooled stream 118 contains n-para?ins in liquid phase, and

Water, hydrogen, and propane in vapor phase. Liquid and

Note: Oleic acid is shown as typical fatty acid for all illustra
tive reactions. It should be understood by one of ordinary skill
in the art that the fatty acid composition may vary consider

ably in feed stocks of different origin.

DETAILED DESCRIPTION OF THE INVENTION

[0022] Referring noW to the drawings, and more particu

larly to FIG. 1, shoWn therein is a schematic of the operation
of the process in accordance With the present invention as

vapor are separated in a drum 119. A vapor stream 12011 is

cooled in an air cooler 122 to condense the light hydrocarbons

(including propane) and Water. A three phase stream 123 is
separated in a drum 124 into a hydrogen-rich vapor stream
12511, a paraf?n product stream 125b, and Water 1250. The
Water is combined With HDO Water 1130 from reactor 108
and sent to offsite Water treatment for use or disposal. Paraf?n
product streams 12019 and 1251) may be combined into a

described herein. A biofeed 101, containing fatty acids and/or

fatty acid esters, is pressurized to betWeen about 1,200-1,800
psig using pump 102. A pressurized biofeed 103 is combined

single stream 126. The n-para?ins in stream 126 may be

hydroisomeriZed to isopara?inic diesel and/ or hydrocracked
to isopara?inic kerosene jet fuel. The LPG and naphtha co
products may then be separated. A ?xed-bed reactor similar to
the HDO reactors described herein may be used for hydroi

With a recycled hydrogen stream 134 (compressed to the same

pressure) such that a combined reactor feed 104 is heated

Group VIIIB metals such as platinum, palladium, and nickel

through a feed-effluent heat exchanger 105 before further

heating to the desired reactor inlet temperature of betWeen
about 600-6500 F. in heater 106. A preheated feed stream 107

rided alumina, silica, ferrierite, ZSM-12, ZSM-21, SAPO-11,

enters a ?rst stage HDO reactor 108. The ?rst stage HDO

reactor 108 is packed With a high pore capacity alumina

impregnated With a loW activity hydrogenation metal. In addi
tion to alumina, silica, aluminum phosphate, and combina
tions of these, may also be used. Suitable active metals for this

type of catalyst include molybdenum, chromium, tungsten,

copper, and others from Group VIIB, VIIB, and IB of the

someriZation/hydrocracking. Suitable catalysts include

on amorphous or crystalline supports such as alumina, ?uo
and SAPO-31.

[0026] The desired hydrogen concentration in a recycle

treat gas 133 may be reached by purging (stream 127) some of

the recycle hydrogen and replacing that With makeup hydro

gen (stream 132). To reduce the purge/recycle ratio, hydro
gen-rich vapors 121 may be processed through a puri?cation
unit 129. Impurities such as hydrogen sul?de, ammonia, car
bon dioxide, and carbon monoxide present in recycle treat gas

US 2009/0163744 A1

Jun. 25, 2009

128 are thus removed in unit 129 to provide high purity

hydrogen treat gas 130 for HDO reaction Scrubbers (absorp
tion columns) are commonly used for this application.
Makeup hydrogen gas 132 is pressurized in compressor 131a
and combined With treat gas 130 in recycle compressor 13119

TABLE I-continued
Fatty Acid Distribution of Feedstock (Wt %)
015:1
C16:1
017:1
018:1
018:2
018:3
020:1
020:2+

to provide the treat gas for the HDO reactors.

[0027] Referring to FIG. 2, shoWn therein is another

embodiment of the operation of the process generally in
accordance With the invention as described herein except that
the Water from the ?rst stage HDO reactor 108 is not recov
ered as a liquid e?luent. Instead, Water vapors from both HDO
reactors 108 and 116 are combined as vapor stream 12111 for

<0.1
4.4
0.1
42.4
19.2
1.1
0.8
0.2

condensing in the single air cooler 122. Although a loWer

capital cost embodiment, the Water soluble salts are not
removed With inter-stage Water e?luent. Modi?cations may
be made to the tWo-stage HDO process to account for changes
in feed quality as shoWn in FIG. 2. For example, if the feed is
de?cient in organic sulfur, a sulfur agent must be introduced
to keep the catalysts in the sul?de state. As another example,

hydrogen quench may be employed to reduce the temperature

rise across each bed. Additionally, removal of Water betWeen
the tWo reaction stages provides an effective means of remov

ing reaction heat and decreases Water partial pressure (and

increases the hydrogen partial pressure) Which is knoWn to
increase catalyst stability. It should be understood by one of
ordinary skill in the art that such modi?cations are Within the

TABLE 11
Performance of First Stage HDO Reactor (Note a)
First Stage HDO Reactor Temp
500 F.

600 F.

650 F.

72.3
1.26

37.9
7.35

1.65
79.1
0.87
0.851

26.5

Product Analysis
Acid number(mg KOH/g)
% Unsaponi?ables
% Free fatty acids

38.05

19.95

% Triglycerides (Note b)

5 8.48

5 6.73

5.34
57.2
2.81
16.5

ICP Analysis (Wppm)

spirit of the inventive tWo-stage HDO process.

[0028] The tWo-step HDO process solves other process
needs not met by a single stage adiabatic ?xed-bed reactor
typically used in the prior art. The tWo-step process provides
an effective Way of removing heat from the exothermic HDO
conversion, reduces Water partial pressure, and prevents con

Water
CO
C02

taminants from deactivating/plugging the high activity cata

Feed

Iron

142

42.7

25.1

Phosphorus

193

31.6

91.3

Group I + II metals

987

358

439

75.9
508

Byproduct yields (Wt %)

4
4
4

1.23
0.23
0.0

5.58
0.45
0.15

6.6
0.72
0.70

lyst bed. Furthermore, by selectively converting the free fatty

Notes:

acids in the ?rst stage HDO reactor 108, the corrosive load on
the second stage HDO reactor 116 and catalyst is eliminated.

(a) All runs at 1600 psig pressure, 2 LHSV feed rate, and 7,500 scf/bbl gas
to-oil ratio
(b) GC retention time 22-25 min.

[0029] In order to further illustrate the present invention,

the folloWing examples are given. HoWever, it is to be under
stood that the examples are for illustrative purposes only and
are not to be construed as limiting the scope of the subject
invention.
EXAMPLES

[0031]

A 100 cc pilot plant reactor Was ?lled With a bottom

bed of loW activity molybdenum oxide catalyst and a top bed

of inerts. The bottom bed consisted of 28.2 g TK-709 catalyst
from Haldor Topsoe (ground and sieved to 20+100 mesh
siZe) and 37.8 g of inert glass beads (70+100 mesh). The top
bed Was 19.2 g TK-30 alumina inert reactor topping media

from Haldor Topsoe and 25.2 g glass beads.

Example 1
TWo-Stage HDO Process

[0032] The molybdenum catalyst Was sul?ded by dimethyl

disul?de diluted in ultra-loW sulfur diesel solvent. The maxi

[0030] A blend of broWn grease, yelloW grease, poultry oil,

?oatation grease, and lard Was prepared. The fatty acid pro?le
of the blend is summariZed in Table I. Additional properties,
including free fatty acid and contaminants concentration, are
listed in Table II under the heading Feed.

mum sul?ding temperature was 7000 F. at Which the reactor

Was held for 16 hours. The reactor Was then cooled doWn to

TABLE I

psig H2 pressure While temperature Was ramped to target

400 F. With solvent still ?oWing. Liquid How Was at 2 LHSV

(active catalyst basis) and hydrogen ?oW at 7,000-8,000 scf/

bbl throughout this sul?ding and catalyst break-in period.
[0033]

Fatty Acid Distribution of Feedstock (Wt %)

The feed Was pumped through the reactor at 1600

condition for the experiment. The test conditions and results

are summariZed in Table II.

C12:0
C14:0
C15:0
C16:0
C17:0
C18:0
C20:0
C22:0
C14:1

0.1
0.9
0.1
21
0.3
8.5
0.6
0.1
0.2

[0034] The drop in acid number suggests conversion of free

fatty acids starting beloW 500 F. and virtually complete at
650 F. The gas chromatogram (GC) of the reactor product
stream indicated complete conversion of the triglyceride at
650 F. Further analysis using GC-MS, GC With a para?in
ole?n-alcohol standard, and FTIR spectroscopy con?rmed
that the products of triglyceride conversion Were fatty alco
hols and diesters.

US 2009/0163744 A1

[0035]

Jun. 25, 2009

The product of the 6000 F. and the 650 F. conver

sion runs above Were combined and used as feed to another

100 cc reactor. The reactor contained a NiMo catalyst and Was

sul?ded according to the procedure described earlier in this

What is claimed is:

1. A process for producing a hydrocarbon from biomass,

comprising the steps of:

example. TWo runs at different temperatures and space veloci

providing a feed stream containing biomass having free

fatty acids, fatty acid esters, or combinations thereof;

ties Were conducted and are summariZed in Table 111.

heating the feed stream in the presence of a ?rst catalyst to

produce a partially hydrodeoxygenated stream; and

heating the partially hydrodeoxygenated stream in the

TABLE 111

presence of a second catalyst to produce an effluent

Performance of Second Stage HDO Reactor (Notes a b)

LHSV (hrl)
WABT (F.)

gas-to-oil ratio (scf/bbl)

Run 1

Run 2

3
680

1.5
700

16,000

Speci?c gravity
Water yield (Wt %)

0.805
4.6

10,000
0.795
7.8

Notes:

(a) Reactor feed composite of ?rst stage HDO reactor from 600 and 650 F.

(see Table I)
(b) Both runs at 1600 psig pressure

[0036]

Run 2 resulted in complete conversion to n-paraf

?ns, as suggested by speci?c gravity and GC (FIG. 3). The

HDO ef?ciency Was calculated by ratio of n-C18 to sum of

n-C17 and n-C18. (Since there is very little C17 fatty acid in
the triglyceride/ fatty acid feedstock, all n-C17 must be
formed via DCO.) The HDO ef?ciency Was thus calculated to
be 80%.

Example 2
One-Stage Hdo Process
[0037]

A 100 cc isothermal tubular reactor Was ?lled With

80 cc of NiMo-on-alumina catalyst pellets (commercial cata

lyst from Catalyst Trading Company, Ltd., Houston) and

+70-100 mesh glass beads. The catalyst had the same MoO3/
NiO loading and surface area as the NiMo catalyst of
Example 1 and Was sul?ded according to the method
described therein. The reactor Was operated at 700 F and

1,200-1,600 psig H2 pressure With both vegetable oils and

animal fat feeds. The feed ?oW rate Was 1 LHSV (active

catalyst basis), With about 10,000 scf/bbl H2-to-feed ratio.

The n-para?in products obtained Were analyZed by GC and
the HDO ef?ciency Was calculated according to the method
described in Example 1 . The HDO ef?ciencies Were 630% for

talloW (beef fat), 58% for palm oil, and 66% for canola oil.
[0038] From the above description, it is clear that the
present invention is Well adapted to carry out the objects and
to attain the advantages mentioned herein as Well as those

inherent in the invention. While presently preferred embodi

ments of the invention have been described for purposes of
this disclosure, it Will be understood that numerous changes
may be made Which Will readily suggest themselves to those
skilled in the art and Which are accomplished Within the spirit
of the invention disclosed and claimed.

stream containing the hydrocarbon.

2. The process of claim 1 Wherein the biomass includes

vegetable oils, animal fats, restaurant greases, Waste indus

trial frying oils, tall oil fatty acid, or combinations thereof.
3. The process of claim 1 Wherein the ?rst catalyst is a loW

activity hydrogenation metal.

4. The process of claim 3 Wherein the metal is selected from

the group consisting of molybdenum, copper, iron, chro

mium, and tungsten.
5. The process of claim 1 Wherein the second catalyst is
bimetallic.
6. The process of claim 5 Wherein the bimetal is selected

from the group consisting of NiMo, CoMo, and NiW.

7. The process of claim 1 Wherein the feed stream is heated
to a temperature in a range of about 600 to about 6500 F.

8. The process of claim 1 Wherein the partially hydrode

oxygenated stream is heated to a temperature of about 550 F.

9. The process of claim 1 further comprising the step of:

isomeriZing the hydrocarbon of the effluent stream to pro
vide an isoparaf?n.
10. A process for hydrodeoxygenation, comprising the
steps of:
cracking a triglyceride into at least one fatty alcohol and at
least one diester; and
hydrodeoxygenating the at least one fatty alcohol and the at
least one diester into at least one hydrocarbon.

11. The process of claim 10 Wherein the triglyceride is

cracked in the presence of a loW activity catalyst.
12. The process of claim 10 Wherein free fatty acids are
converted to fatty alcohols and hydrocarbons in the presence
of a loW activity catalyst.
13. The process of claim 11 Wherein the loW activity cata

lyst is selected from the group consisting of molybdenum,

copper, iron, chromium, and tungsten.
14. The process of claim 10 Wherein the at least one fatty
alcohol and the at least one diester are hydrodeoxygenated in

the presence of a high activity catalyst.

15. The process of claim 13 Wherein the high activity
catalyst is selected from the group consisting of NiMo,
CoMo, and NiW.
16. The process of claim 10 further comprising the step of:
isomeriZing the at least one hydrocarbon to at least one