U.S. patent application number 13/578225 was filed with the patent office on 2012-12-20 for catalyst for producing hydrogenated biodiesel and method of producing the same.
This patent application is currently assigned to SK ENERGY CO., LTD.. Invention is credited to Hee Jung Jeon, Sang Jun Ju, Do Woan Kim, Gyung Rok Kim, Sang Il Lee, Jae Wook Ryu.
Application Number | 20120323056 13/578225 |
Document ID | / |
Family ID | 44378882 |
Filed Date | 2012-12-20 |
United States Patent
Application |
20120323056 |
Kind Code |
A1 |
Lee; Sang Il ; et
al. |
December 20, 2012 |
CATALYST FOR PRODUCING HYDROGENATED BIODIESEL AND METHOD OF
PRODUCING THE SAME
Abstract
Disclosed herein is a catalyst for producing biodiesel,
including a carrier having water resistance and an active component
supported on the carrier and used in a hydrotreating reaction or a
decarboxylation reaction. Since the catalyst for producing
biodiesel includes a carrier having strong water resistance, the
deactivation of the catalyst due to the water produced through a
process of producing HBD can be prevented, thus remarkably
improving the long term stability of a catalyst.
Inventors: |
Lee; Sang Il; (Yuseong-gu,
KR) ; Kim; Do Woan; (Yuseong-gu, KR) ; Jeon;
Hee Jung; (Yuseong-gu, KR) ; Ju; Sang Jun;
(Sasang-gu, KR) ; Ryu; Jae Wook; (Yuseong-gu,
KR) ; Kim; Gyung Rok; (Yuseong-gu, KR) |
Assignee: |
SK ENERGY CO., LTD.
Seoul
KR
SK INNOVATION CO., LTD.
Seoul
KR
|
Family ID: |
44378882 |
Appl. No.: |
13/578225 |
Filed: |
October 20, 2010 |
PCT Filed: |
October 20, 2010 |
PCT NO: |
PCT/KR2010/007184 |
371 Date: |
September 7, 2012 |
Current U.S.
Class: |
585/16 ; 502/182;
502/208; 502/305; 502/313; 502/315; 502/321; 502/349; 502/350;
502/353; 585/240; 585/253 |
Current CPC
Class: |
B01J 23/462 20130101;
B01J 23/888 20130101; Y02E 50/10 20130101; B01J 23/883 20130101;
B01J 38/18 20130101; B01J 23/44 20130101; B01J 23/468 20130101;
C10G 3/46 20130101; C10G 3/50 20130101; C10L 1/08 20130101; C10L
2200/0469 20130101; Y02E 50/13 20130101; C10L 2290/06 20130101;
B01J 37/0201 20130101; B01J 23/34 20130101; C10G 3/44 20130101;
B01J 23/28 20130101; B01J 23/8877 20130101; B01J 23/755 20130101;
C11C 3/126 20130101; B01J 23/42 20130101; B01J 23/882 20130101;
Y02P 30/20 20151101; B01J 23/885 20130101; C10L 1/026 20130101;
B01J 21/066 20130101; B01J 23/30 20130101; B01J 23/75 20130101;
B01J 21/063 20130101; B01J 23/745 20130101 |
Class at
Publication: |
585/16 ; 502/321;
502/305; 502/315; 502/313; 502/349; 502/350; 502/182; 502/208;
502/353; 585/240; 585/253 |
International
Class: |
B01J 23/28 20060101
B01J023/28; B01J 23/883 20060101 B01J023/883; B01J 23/882 20060101
B01J023/882; B01J 21/06 20060101 B01J021/06; C10L 1/04 20060101
C10L001/04; B01J 29/83 20060101 B01J029/83; B01J 23/20 20060101
B01J023/20; B01J 23/888 20060101 B01J023/888; C10G 3/00 20060101
C10G003/00; B01J 23/30 20060101 B01J023/30; B01J 21/18 20060101
B01J021/18 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 11, 2010 |
KR |
10-2010-0012711 |
Claims
1. A catalyst for producing biodiesel, comprising a carrier having
water resistance and an active component supported on the carrier
and used in a hydrotreating reaction or a decarboxylation
reaction.
2. The catalyst for producing biodiesel according to claim 1,
wherein the catalyst comprises a group VIB metal as the active
component supported on the carrier.
3. The catalyst for producing biodiesel according to claim 2,
wherein the catalyst further comprises a group VIIB metal or a
group VIII metal as the active component supported on the
carrier.
4. The catalyst for producing biodiesel according to claim 1,
wherein the carrier is selected from among zirconia, titania,
aluminum phosphate, niobia, zirconium phosphate, titanium
phosphate, silicon carbide, carbon and mixtures thereof.
5. The catalyst for producing biodiesel according to claim 2,
wherein the group VIB metal is Mo or W, and the amount thereof is
0.1.about.70 wt % among total active agent.
6. The catalyst for producing biodiesel according to claim 3,
wherein the group VIII metal is Ni, Pd or Pt, and the amount
thereof is 0.about.60 wt % among total active agent.
7. The catalyst for producing biodiesel according to claim 3,
wherein the group VIIB metal is Co, Ru, Fe, Mn or Ir, and the
amount thereof is 0.about.60 wt % among total active agent.
8. The catalyst for producing biodiesel according to claim 2,
wherein the group VIB metal is present in an amount of 1.about.40
wt % based on the carrier.
9. The catalyst for producing biodiesel according to claim 3,
wherein the group VIII metal or group VIIB metal is present in an
amount of 0.about.20 wt % based on the carrier.
10. A method of producing biodiesel through a hydrotreating
reaction or a decarboxylation reaction in the presence of the
catalyst of claim 1.
11. The method of producing biodiesel according to claim 10,
wherein biomass, such as plant oil, plant fat, animal fat, fish
oil, recycled fat, plant fatty acids, animal fatty acids or
mixtures thereof, is used as a feed.
12. The method of producing biodiesel according to claim 11,
wherein the plant fat, animal fat or recycled fat includes
triglycerides, each chain of which is composed of 1.about.28 carbon
atoms, and each of the plant fatty acids or animal fatty acids has
1.about.28 carbon atoms.
13. The method of producing biodiesel according to claim 11,
wherein, in addition to the biomass, one or more hydrocarbon
mixtures (0-99%) are used as the feed.
14. The method of producing biodiesel according to claim 13,
wherein the hydrocarbon includes kerosene, diesel, light gas oil
(LGO), and recycled HBD.
15. The method of producing biodiesel according to claim 10, the
method comprises the steps of: pretreating a feed through
hydrotreatment; separating unreacted hydrogen after a
hydrodeoxygenation reaction to form hydrocarbons; and cooling,
separating and isomerizing the formed hydrocarbons.
16. Biodiesel produced by the method of claim 10.
Description
TECHNICAL FIELD
[0001] The present invention relates to a catalyst for producing
biodiesel and a method of producing biodiesel using the same, and,
more particularly, to a catalyst which is used to produce biodiesel
and has strong water resistance.
BACKGROUND ART
[0002] The necessities of developing alternative energy resources
and reducing greenhouse gas emissions have been on the rise all
over the world in correspondence with the high oil price, and thus
the development of bioenergy resources has been actively conducted.
Moreover, all over the world, the supply of biodiesel is increasing
according to the improvement of taxation systems and laws, and thus
the market related to bioenergy becomes bigger at a growth rate of
8.about.12% per year.
[0003] A typical technology of producing a diesel fraction from
biomass is a technology of producing fatty acid methyl ester
(FAME). Fatty acid methyl ester (FAME), which is an alternative
energy source produced from biomass, is advantageous in that its
cetane number is higher than that of a diesel fraction produced
from mineral oil, but is disadvantageous in that its oxidation
stability is low and its production costs are high.
[0004] As a next-generation alternative energy source, hydrogenated
biodiesel (HBD), which is produced by directly hydrogenating
triglycerides through a hydrotreating reaction, has been proposed.
The production cost of hydrogenated biodiesel (HBD) is higher than
that of diesel produced from mineral oil, but is lower than that of
fatty acid methyl ester (FAME). Further, the oxidation stability of
hydrogenated biodiesel (HBD) is relatively high because it is
produced through a hydrotreating reaction.
[0005] Furthermore, hydrogenated biodiesel (HBD) is advantageous in
that it can be used to produce high-grade diesel oil having a
cetane number of approximately 100, and in that it is excellent in
terms of energy efficiency or greenhouse gas emission reduction
compared to mineral oil or FAME.
[0006] However, the biggest problem in a HBD producing process is
that it is difficult to maintain the activity of a catalyst for a
long period of time. Currently, a commercial hydrotreating catalyst
is used in a HBD producing process, but the commercial
hydrotreating catalyst is disadvantageous in that its carrier is
leached out by water, which is a byproduct formed in the HBD
catalytic reaction, and thus its catalytic activity is gradually
decreased. In order to solve this problem, to date, a method of
minimizing the deactivation of the hydrotreating catalyst by
changing operation conditions so that a small amount of
triglycerides is added to mineral oil without using only the
triglycerides as a feed has been used.
[0007] HBD producing processes are largely classified into two
types. One is a HBD producing process including only a
hydrotreating process, and the other is a HBD producing process
including a hydrotreatment process and an isomerization
process.
[0008] In the HBD producing process, the hydrotreatment process is
a process of hydrotreated fat or fatty acid through a hydrotreating
reaction. This hydrotreatment process is similar to a hydrotreating
process, a deoxygenation process, a hydrodeoxygenation process, a
decarboxylation process or a decarbonylation process. That is, in
the HBD producing process, the decarboxylation or decarbonylation
process is similarly used together with the hydrotreatment process
because one carbon atom in the fat or fatty acid is hydrotreated in
the decarboxylation or decarbonylation process.
[0009] Generally, the plant oil used as a feed for producing
biodiesel is composed of triglycerides. When this ester type
triglyceride is hydrotreated, a paraffin of C15.about.C18 can be
obtained. Since the obtained paraffin has a boiling point
corresponding to that of diesel oil, it can be used as biodiesel.
However, since this paraffin-based biodiesel has a high pour point,
its low-temperature stability may be improved through an
isomerization reaction in order to maintain it in a liquid state
even at low temperature. Currently, since the used amount of
biodiesel is only several percent (%) of the used amount of
conventional petroleum diesel, if necessary, the biodiesel may be
selectively isomerized.
[0010] Technologies of producing HBD using hydrotreatment are
disclosed in the following documents. U.S. Pat. No. 4,992,605
discloses a process of producing biodiesel, in which crude palm oil
is used as a feed and in which CoMo, NiMo or a transition metal is
used as a hydrotreating catalyst.
[0011] U.S. Patent Application Publication NO. 2007-0175795
discloses a process of producing hydrogenated biodiesel, in which
Ni, Co, Fe, Mn, W, Ag, Au, Cu, Pt, Zn, Sn, Ru, Mo, Sb, V, Jr, Cr or
Pd is used as a catalyst for hydrotreating triglyceride.
[0012] U.S. Pat. No. 7,232,935 discloses a process of producing
HBD, in which plant oil, as a feed, is formed into HBD by
sequentially performing a hydrotreating process and an
isomerization process.
[0013] U.S. Pat. No. 7,279,018 discloses a process of producing
HBD, in which the hydrotreated and isomerized HBD is mixed with
0.about.20% of an antioxidative material to form a product.
[0014] U.S. Patent Application Publication NO. 2007-0010682
discloses a process of producing HBD including a hydrotreatment
process and an isomerization process, in which a raw material
includes 5 wt % or more of free fatty acid and a diluent, and the
ratio of diluent:raw material is 5.about.30:1.
[0015] U.S. Patent Application Publication NO. 2006-0207166
discloses a process of producing HBD including a hydrotreatment
process and an isomerization process, in which the hydrotreatment
process and isomerization processes are simultaneously conducted
using a catalyst in which an acidic carrier is supported with
metals.
[0016] As described above, currently, HBD is being produced by
directly applying a commercial hydrotreating catalyst to a process
of producing HBD or by the catalyst that reformed commercial
hydrotreating catalyst to the process of producing HBD. The
conventionally commercial hydrotreating catalyst used alumina,
silica-alumina, etc, as carrier.
[0017] However, when the commercial hydrotreating catalyst was used
in the process of producing HBD, there was a serious problem in
that the catalyst has low long term stability, although it has
seemed initially high activity and selectivity.
[0018] Prior arts have many efforts to overcome the problem but
have been limitedly solved through process operation control, such
as a process of recycling the reacted HBC fraction but prior arts
cannot have found the fundamental causes of low long term catalyst
stability.
DISCLOSURE OF INVENTION
Technical Problem
[0019] Accordingly, the present invention has been made to overcome
the above problems, and the present invention provides a catalyst
for producing biodiesel, which has high long term stability and
activity.
[0020] Further, the present invention provides a method of
producing biodiesel using the catalyst.
[0021] Furthermore, the present invention provides biodiesel
produced by the method.
Solution to Problem
[0022] In order to solve the above problems, an aspect of the
present invention provides a catalyst for producing biodiesel,
including a carrier having water resistance and an active component
supported on the carrier and used in a hydrotreting reaction or a
decarboxylation reaction.
[0023] The catalyst may include a group VIB metal as the active
component supported on the carrier.
[0024] The catalyst may include a group VIIB metal or a group VIII
metal as the active component supported on the carrier.
[0025] The carrier may be selected from among zirconia, titania,
aluminum phosphate, niobia, zirconium phosphate, titanium
phosphate, silicon carbide, carbon and mixtures thereof.
[0026] The group VIB metal may be Mo or W, and the amount thereof
may be 0.1.about.70 wt % among total active agent.
[0027] The group VIII metal may be Ni, Pd or Pt, and the amount
thereof may be 0.about.60 wt % among total active agent.
[0028] The group VIIB metal may be Co, Ru, Fe, Mn or Ir, and the
amount thereof may be 0.about.60 wt % among total active agent.
[0029] The group VIB metal may be present in an amount of
1.about.40 wt % based on the carrier.
[0030] The group VIII metal or group VIIB metal may be present in
an amount of 1.about.20 wt % based on the carrier.
[0031] Another aspect of the present invention provides a method of
producing biodiesel through a hydrotreating reaction or a
decarboxylation reaction in the presence of the catalyst for
producing biodiesel.
[0032] In the method, biomass, such as plant oil, plant fat, animal
fat, fish oil, recycled fat, plant fatty acids, animal fatty acids
or mixtures thereof, may be used as a feed.
[0033] The plant fat, animal fat or recycled fat includes
triglycerides, each chain of which is composed of 1.about.28 carbon
atoms, and each of the plant fatty acids or animal fatty acids has
1.about.28 carbon atoms.
[0034] In the method, in addition to the biomass, one or more
hydrocarbon mixtures (0.about.99%) may be used as the feed.
[0035] The method comprises the steps of: pretreating a feed
through hydrotreatment; separating unreacted hydrogen after a
hydrodeoxygenation reaction to form hydrocarbons; and cooling,
separating and isomerizing the formed hydrocarbons.
[0036] Still another aspect of the present invention provides
biodiesel produced by the method.
Advantageous Effects of Invention
[0037] As described above, the catalyst for producing biodiesel
according to the present invention is advantageous in that it has
high long-term activity and is not leached, thus improving long
term stability.
BRIEF DESCRIPTION OF DRAWINGS
[0038] The above and other objects, features and advantages of the
present invention will be more clearly understood from the
following detailed description taken in conjunction with the
accompanying drawings, in which:
[0039] FIG. 1 is a view showing a process of producing HBD when
only plant oil is used as a feed; and
[0040] FIG. 2 is a view showing a process of producing HBD when a
mixture of plant oil and hydrocarbons is used as a feed.
BEST MODE FOR CARRYING OUT THE INVENTION
[0041] Hereinafter, preferred embodiments of the present invention
will be described in detail with reference to the attached
drawings.
[0042] When the commercial hydrotreating catalyst is used to
produce HBD, it is difficult to produce HBD for a long period of
time since the hydrotreating catalysts has become deactivate. As
previous stated, prior arts have many efforts to overcome the
problem but has been limitedly solved through process operation
control, such as a process of recycling the reacted HBC fraction
but a catalyst specified in the HBD reaction has not been developed
yet.
[0043] The present inventors found the fundamental cause of
lowering long-term catalyst activity that the side reaction in the
process of HBD formation reaction produced the water which leached
out the active sites of catalyst thus resulted in the deactivation
of catalyst.
[0044] Therefore, the present inventors minimized the deactivation
of the catalyst by introducing active sites into a water-resistant
carrier having a hydrogenation function. Further, in the course of
the present research, it was found that the hydrotreating catalyst
manufactured using the technology of the present invention
maintains higher long-term catalyst activity than that of the
commercial hydrotreating catalyst by two fold or more in the
process of producing HBD.
[0045] Plant oil mainly consists of triglycerides. As below figure,
in the general hydrotreating process, triglycerides reacted by
hydrogen produces normal paraffin such as C14-C18 and byproducts
such as propane, H2O, CO, CO2.
##STR00001##
[0046] The paraffin produced at this time is C14-C18, and it is
commonly named as HBD since it is diesel oil. The above produced
H2O unavoidably results in dissolving the catalyst. When Group
III+Group IV metal/carrier catalyst of the commercial hydrotreating
catalyst is used, H2O is produced with rate of about 10 wt %. After
a while a small amount of water does not influence the leaching out
of catalyst carrier very much, increased amount of water causes the
carrier to be leached out and thus the catalyst to be
deactivated.
[0047] Accordingly, the present invention has been made to overcome
the above problems, and the present invention provides a catalyst
for producing biodiesel, which has high long term stability and
activity.
[0048] The present invention provides a catalyst for producing
biodiesel, including a carrier having water resistance and an
active component supported on the carrier and used in a
hydrotreating reaction or a decarboxylation reaction.
[0049] The carrier used in the present invention is selected from
among zirconia, titania, aluminum phosphate, niobia, zirconium
phosphate, titanium phosphate, silicon carbide, carbon and mixtures
thereof.
[0050] The present invention provides a catalyst for producing HBD
(hydrogenated biodiesel), which is used to produce a diesel
fraction from biomass through a hydrotreating reaction or a
decarboxylation reaction, and which is a catalyst formed by adding
an active material having a hydrogenation function or a
decarboxylation function to a carrier having strong water
resistance, such as zirconia, titania, aluminum phosphate, niobia,
zirconium phosphate, titanium phosphate, silicon carbide, carbon
and mixtures thereof or the like. In the catalyst of the present
invention, a carrier having strong water resistance is used, so
that the deactivation of the catalyst due to the water produced
through a process of producing HBD can be prevented, thereby
remarkably improving the long term stability of the catalyst.
[0051] The catalyst used in the present invention can be applied to
a hydrotreating reaction or a decarboxylation reaction using an
alumina declining durability of carrier due to generated water as
well as to a process of producing HBD.
[0052] When the catalyst of the present invention is used in a
process of producing HBD, the catalyst used in a hydrotreating
reaction or a decarboxylation reaction can be used in the process
of producing HBD without limitation, and the catalyst in which a
carrier is supported with a group VIB metal as an active component
can also be used in the process of producing HBD.
[0053] Further, in the catalyst of the present invention, a carrier
having strong water resistance can be supported with a group VIB
metal or a group VIIB metal as another active component in addition
to the group VIB metal.
[0054] As the active component used in the present invention, the
group VIB metal may be Mo or W, the group VIII metal may be Ni, Pd
or Pt, and the group VIIB metal may be Co, Ru, Fe, Mn or Ir, but
the present invention is not limited thereto.
[0055] The catalyst of the present invention includes 0.1.about.70
wt % of a group VIB metal as an active component. When the amount
of the group VIB metal included in the catalyst is less than 0.1 wt
%, the activity of the catalyst is very low, thus the catalyst
cannot serve as a catalyst. When the amount thereof is more than 70
wt %, it is difficult to support the group VIB metal on the
catalyst in an oxidation state. Preferably, the amount of the group
VIB metal may be 1.about.40 wt %.
[0056] Further, the catalyst of the present invention includes
0.about.60 wt % of a group VIII metal or a group VIIB metal as an
active component. When the amount of the group VIII metal or group
VIIB metal is more than 60 wt %, it is difficult to support the
group VIII metal or group VIIB metal on the catalyst. Preferably,
the amount of the group VIII metal or group VIIB metal is
0.about.20 wt %.
[0057] In the process of producing biodiesel according to the
present invention, biomass, such as plant oil, plant fat, animal
fat, fish oil, recycled fat, plant fatty acids, animal fatty acids
or mixtures thereof, can be used as a feed.
[0058] As the plant fat, animal fat or recycled fat, fat including
triglycerides, each chain of which is composed of 1.about.28 carbon
atoms may be used, and, as the plant fatty acids or animal fatty
acids, fatty acids having 1.about.28 carbon atoms may be used, but
the present invention is not limited thereto.
[0059] In the process of producing biodiesel, in addition to the
biomass, one or more hydrocarbon mixtures (0.about.99%) may be used
as a feed. This hydrocarbon may include kerosene, diesel, light gas
oil (LGO), and recycled HBD, but the present invention is not
limited thereto.
[0060] The process of producing biodiesel may include the steps of:
pretreating a feed through hydrotreatment; separating unreacted
hydrogen after a hydrodeoxygenation reaction to form hydrocarbons;
and cooling, separating and isomerizing the formed hydrocarbons. If
necessary, one or two steps may be added or omitted.
[0061] A process of producing HBD using only plant oil as a feed is
shown in FIG. 1, but is not limited thereto.
[0062] FIG. 2 is a view showing a process of producing HBD when a
mixture of plant oil and hydrocarbons is used as a feed. The
process of producing HBD using the mixture of plant oil and
hydrocarbons is different from the process of producing HBD using
the only plant oil in the point that a fractionator for separating
hydrocarbons is required.
[0063] In the process of producing HBD, a mixture in which 1% of
dimethyl disulfide (DMDS) is mixed with plant oil is also used as a
feed. This feed is simultaneously introduced into a HBD reactor
together with hydrogen, and then hydrotreated to form a reaction
product. The reaction product is distilled in a stripper and then
fractionated according to boiling point. Thus, among the
fractionated reaction product, HBD is selectively extracted, and
others are recycled.
MODE FOR THE INVENTION
[0064] Hereinafter, a catalyst for producing HBD and a method of
producing biodiesel through a hydrotreating process using the
catalyst will be described in detail with reference to the
following Examples.
EXAMPLES
Example 1
Preparation of a Mo/ZrO.sub.2Catalyst
[0065] A catalyst containing about 10 wt % of molybdenum (Mo) was
prepared using a zirconia (ZrO2) carrier having a diameter of 1
mm.
[0066] Ammonium heptamolybdate tetrahydrate (hereinafter, referred
to as "AHM") was used a molybdenum (Mo) precursor. A zirconia
(ZrO2) carrier was impregnated with an aqueous solution formed by
dissolving AHM in distilled water, dried at a temperature of
150.degree. C. for 2 hours, and then continuously calcined at a
temperature of 500.degree. C. for 2 hours to prepare a Mo/ZrO.sub.2
catalyst (here, in addition to AHM, various types of molybdenum
(Mo) precursors may be used, and the molybdenum (Mo) precursor is
not limited to AHM).
[0067] 6 cc of the Mo/ZrO.sub.2 catalyst prepared through the above
procedures was charged in a cylindrical reactor, and then heated to
a temperature of 400.degree. C. while introducing hydrogen (H2)
into the cylindrical reactor at a flow rate of 16 cc/min with R-LGO
including 3 wt % of DMDS at the flow rate of 0.08 cc/min and a
reaction pressure of 45 bars, and then pretreated for 3 hours at a
temperature of 400.degree. C.
[0068] Subsequently, as a feed, soybean oil including 1% of
dimethyl disulfide (DMDS) was reacted at a reaction rate of 0.1
cc/min (LHSV=1) using the pretreated Mo/ZrO.sub.2 catalyst under
the conditions of a reaction temperature of 350.degree. C., a
reaction pressure of 30 bars and a hydrogen flow rate of 100
cc/min. Sampling was conducted every 8 hours to obtain reaction
products. The patterns of the obtained reaction products were
observed through simulated distillation, and whether the
Mo/ZrO.sub.2 catalyst was leached was confirmed through ICP
analysis. The results thereof are given in Table 1 and Table 2.
Example 2
Preparation of a NiMo/ZrO.sub.2Catalyst
[0069] A catalyst containing about 10 wt % of molybdenum (Mo) and
about 3 wt % of nickel (Ni) was prepared using a zirconia (ZrO2)
carrier having a diameter of 1 mm. Ammonium heptamolybdate
tetrahydrate (hereinafter, referred to as "AHM") was used a
molybdenum (Mo) precursor, and nickel nitrate hexahydrate
(hereinafter, referred to as "NNH") was used as a nickel (Ni)
precursor. Here, various types of molybdenum (Mo) precursors and
various types of nickel (Ni) precursors may be used, and the
molybdenum (Mo) precursor and nickel (Ni) precursor are not limited
to AHM and NNH, respectively.
[0070] A NiMo/ZrO.sub.2 catalyst was prepared through the following
procedures.
[0071] First, a zirconia (ZrO2) carrier was impregnated with an
aqueous solution formed by dissolving AHM in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a Mo/ZrO.sub.2 catalyst.
[0072] Subsequently, the Mo/ZrO.sub.2 catalyst was impregnated with
an aqueous solution formed by dissolving NNH in distilled water,
dried at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a NiMo/ZrO.sub.2 catalyst.
[0073] Thereafter, subsequent procedures were conducted as in
Example 1, except that the pretreatment of the NiMo/ZrO.sub.2
catalyst was performed at a temperature of 320.degree. C. The
results thereof are given in Table 1 and Table 2.
Example 3
Preparation of a CoMo/TiO.sub.2Catalyst
[0074] A catalyst containing about 10 wt % of molybdenum (Mo) and
about 3 wt % of cobalt (Co) was prepared using a titania (TiO2)
carrier having a diameter of 1 mm. Ammonium heptamolybdate
tetrahydrate (hereinafter, referred to as "AHM") was used a
molybdenum (Mo) precursor, and cobalt nitrate hexahydrate
(hereinafter, referred to as "CNH") was used as a cobalt (Co)
precursor. Here, various types of molybdenum (Mo) precursors and
various types of cobalt (Co) precursors may be used, and the
molybdenum (Mo) precursor and cobalt (Co) precursor are not limited
to AHM and CNH, respectively.
[0075] A CoMo/TiO.sub.2 catalyst was prepared through the following
procedures.
[0076] First, a titania (TiO2) carrier was impregnated with an
aqueous solution formed by dissolving AHM in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a Mo/TiO.sub.2 catalyst.
[0077] Subsequently, the Mo/TiO.sub.2 catalyst was impregnated with
an aqueous solution formed by dissolving CNH in distilled water,
dried at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a CoMo/TiO.sub.2 catalyst.
[0078] Thereafter, subsequent procedures were conducted as in
Example 2. The results thereof are given in Table 1 and Table
2.
Example 4
Preparation of a NiW/TiO.sub.2Catalyst
[0079] A catalyst containing about 10 wt % of tungsten (W) and
about 3 wt % of nickel (Ni) was prepared using a titania (TiO2)
carrier having a diameter of 1 mm. Ammonium metatungstate hydrate
(hereinafter, referred to as "AMT") was used a tungsten (W)
precursor, and nickel nitrate hexahydrate (hereinafter, referred to
as "NNH") was used as a nickel (Ni) precursor. Here, various types
of tungsten (W) precursors and various types of nickel (Ni)
precursors may be used, and the tungsten (W) precursor and nickel
(Ni) precursor are not limited to AMT and NNH, respectively.
[0080] A NiW/TiO.sub.2 catalyst was prepared through the following
procedures.
[0081] First, a titania (TiO2) carrier was impregnated with an
aqueous solution formed by dissolving AMT in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a W/TiO.sub.2 catalyst.
[0082] Subsequently, the W/TiO.sub.2 catalyst was impregnated with
an aqueous solution formed by dissolving NNH in distilled water,
dried at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a NiW/TiO.sub.2 catalyst.
[0083] Thereafter, subsequent procedures were conducted as in
Example 2. The results thereof are given in Table 1 and Table
2.
Example 5
Preparation of a NiMo/C Catalyst
[0084] A catalyst containing about 15 wt % of molybdenum (Mo) and
about 5 wt % of nickel (Ni) was prepared using a carbon (C) carrier
having a diameter of 1 mm. Ammonium heptamolybdate tetrahydrate
(hereinafter, referred to as "AHM") was used a molybdenum (Mo)
precursor, and nickel nitrate hexahydrate (hereinafter, referred to
as "NNH") was used as a nickel (Ni) precursor. Here, various types
of molybdenum (Mo) precursors and various types of nickel (Ni)
precursors may be used, and the molybdenum (Mo) precursor and
nickel (Ni) precursor are not limited to AHM and NNH,
respectively.
[0085] A NiMo/C catalyst was prepared as follows.
[0086] A carbon (C) carrier was impregnated with an aqueous
solution formed by dissolving AHM and NNH in distilled water, and
then dried at a temperature of 300.degree. C. for 2 hours to
prepare a NiMo/C catalyst.
[0087] Thereafter, subsequent procedures were conducted as in
Example 2. The results thereof are given in Table 1 and Table
2.
Example 6
Preparation of a NiMo/AlPO4 Catalyst
[0088] A catalyst containing about 15 wt % of molybdenum (Mo) and
about 5 wt % of nickel (Ni) was prepared using a aluminum phosphate
(AlPO4) carrier. Molybdenum (Mo) precursor, and nickel (Ni)
precursor can be used like those of Example 2, respectively.
[0089] A NiMo/AlPO4 catalyst was prepared through the following
procedures.
[0090] First, a aluminum phosphate (AlPO4) carrier was impregnated
with an aqueous solution formed by dissolving AHM and NNH in
distilled water, dried at a temperature of 150.degree. C. for 2
hours, and then pretreated as in Example 2.
[0091] The results thereof are given in Table 1 and Table 2.
Example 7
Preparation of a NiMo/Nb2O5 Catalyst
[0092] A catalyst containing about 7 wt % of molybdenum (Mo) and
about 2 wt % of nickel (Ni) was prepared using a niobium oxide
(Nb2O5) carrier. Molybdenum (Mo) precursor, and nickel (Ni)
precursor can be used like those of Example 2, respectively.
[0093] A NiMo/Nb2O5 catalyst was prepared through the following
procedures.
[0094] First, a aluminum phosphate (AlPO4) carrier was impregnated
with like Example 6 and then pretreated as in Example 2.
[0095] The results thereof are given in Table 1 and Table 2.
Comparative Example 1
Preparation of a NiMo/Al.sub.2O.sub.3Catalyst
[0096] A catalyst containing about 10 wt % of molybdenum (Mo) and
about 3 wt % of nickel (Ni) was prepared using an alumina (Al2O3)
carrier having a diameter of 1 mm. Ammonium heptamolybdate
tetrahydrate (hereinafter, referred to as "AHM") was used a
molybdenum (Mo) precursor, and nickel nitrate hexahydrate
(hereinafter, referred to as "NNH") was used as a nickel (Ni)
precursor. Here, various types of molybdenum (Mo) precursors and
various types of nickel (Ni) precursors may be used, and the
molybdenum (Mo) precursor and nickel (Ni) precursor are not limited
to AHM and NNH, respectively.
[0097] A NiMo/Al2O3 catalyst was prepared through the following
procedures.
[0098] First, an alumina (Al2O3) carrier was impregnated with an
aqueous solution formed by dissolving AHM in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a Mo/Al2O3 catalyst.
[0099] Subsequently, the Mo/Al2O3 catalyst was impregnated with an
aqueous solution formed by dissolving 3.06 g of NNH in distilled
water, dried at a temperature of 150.degree. C. for 2 hours, and
then continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a NiMo/Al2O3 catalyst.
[0100] Thereafter, subsequent procedures were conducted as in
Example 2. The results thereof are given in Table 1 and Table
2.
Comparative Example 2
Preparation of a CoMo/Al.sub.2O.sub.3Catalyst
[0101] A catalyst containing about 10 wt % of molybdenum (Mo) and
about 3 wt % of cobalt (Co) was prepared using an alumina (Al2O3)
carrier having a diameter of 1 mm. Ammonium heptamolybdate
tetrahydrate (hereinafter, referred to as "AHM") was used a
molybdenum (Mo) precursor, and cobalt nitrate hexahydrate
(hereinafter, referred to as "CNH") was used as a cobalt (Co)
precursor. Here, various types of molybdenum (Mo) precursors and
various types of cobalt (Co) precursors may be used, and the
molybdenum (Mo) precursor and cobalt (Co) precursor are not limited
to AHM and CNH, respectively.
[0102] A CoMo/Al2O3 catalyst was prepared through the following
procedures.
[0103] First, an alumina (Al2O3) carrier was impregnated with an
aqueous solution formed by dissolving AHM in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a Mo/Al2O3 catalyst.
[0104] Subsequently, the Mo/Al2O3 catalyst was impregnated with an
aqueous solution formed by dissolving CNH in distilled water, dried
at a temperature of 150.degree. C. for 2 hours, and then
continuously calcined at a temperature of 500.degree. C. for 2
hours to prepare a CoMo/Al2O3 catalyst.
[0105] Thereafter, subsequent procedures were conducted as in
Example 2. The results thereof are given in Table 1 and Table
2.
[0106] From Table 1, in the case of the catalysts prepared using an
alumina (Al2O3) carrier, it can be seen that yields rapidly
decrease with the passage of reaction time although initial
activity is good. In contrast, in the case of the catalysts
prepared using a zirconia (ZrO2) carrier, a titania (TiO2) carrier,
a carbon (C) carrier, aluminum phosphate carrier, or niobia
carrier, as given in Table 1, it can be seen that their initial
activity and long-term stability are excellent compared to those of
the catalysts prepared using an alumina (Al2O3) carrier. In
particular, as given in Table 2, the catalysts prepared using a
zirconia (ZrO2) carrier, a titania (TiO2) carrier, a carbon (C)
carrier, aluminum phosphate carrier, or niobia carrier have
excellent water resistance and do not cause a catalyst dissolving
phenomenon, but in the catalysts prepared using an alumina (Al2O3)
carrier, their catalyst and carrier component are leached out
therefrom and they are rapidly dissolved with the passage of
reaction time.
TABLE-US-00001 TABLE 1 Catalyst/diesel selectivity (%) 1 day 15
days 30 days Mo/ZrO.sub.2 83 84 80 NiMo/ZrO.sub.2 86 88 89
CoMo/TiO.sub.2 84 85 86 NiW/TiO.sub.2 89 89 87 NiMo/C 82 82 81
NiMo/AlPO.sub.4 81 80 80 NiMo/Nb.sub.2O.sub.5 78 78 77
NiMo/Al.sub.2O.sub.3 82 79 74 CoMo/Al.sub.2O.sub.3 82 78 76
TABLE-US-00002 TABLE 2 composition (wppm) 1 day 15 days 30 days
Catalyst Ni Co Mo Zr Ti Al Ni Co Mo Zr Ti Al Ni Co Mo Zr Ti Al
Mo/ZrO.sub.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 NiMo/ZrO.sub.2 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 CoMo/TiO.sub.2 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 NiW/TiO.sub.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
NiMo/C -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- --
NiMo/AlPO.sub.4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
NiMo/Nb.sub.2O.sub.5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
NiMo/Al.sub.2O.sub.3 0 0 0 0 0 0 0 0 0 0 0 57 0 0 1.3 0 0 1670
CoMo/Al.sub.2O.sub.3 0 0 0 0 0 0 0 0 0 0 0 45 0 0 0.5 0 0 1250
[0107] As described above, the catalyst for producing biodiesel
according to the present invention is advantageous in that it has
high long-term activity and is not leached, thus improving long
term stability.
[0108] Although the preferred embodiments of the present invention
have been disclosed for illustrative purposes, those skilled in the
art will appreciate that various modifications, additions and
substitutions are possible, without departing from the scope and
spirit of the invention as disclosed in the accompanying
claims.
* * * * *