Abstract:
The present invention provides a Mo-Bi-Nb based composite metal oxide (with
the proviso that Te is not included); a method for producing (meth)acrylic acid
from at least one reactant selected from the group consisting of propylene,
propane, isobutylene, t-butyl alcohol and methyl-t-butyl ether, in which a Mo-Bi-
Nb based composite metal oxide (with the proviso that Te is not included) is used
as a catalyst; and a reactor used for producing (meth)acrylic acid from at least
one reactant selected from the group consisting of propylene, propane,
isobutylene, t-butyl alcohol and methyl-t-butyl ether, in which a Mo-Bi-Nb based
composite metal oxide (with the proviso that Te is not included) is used as a
catalyst. Further, the present invention provides a method for producing
(meth)acrylic acid from at least one reactant selected from the group consisting
of propylene, propane, isobutylene, t-butyl alcohol and methyl-t-butyl ether by
using a Mo-Bi-Nb based composite metal oxide as a catalyst, without any
additional process of converting (meth)acrolein into (meth)acrylic acid.
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Notices, Deadlines & Correspondence
20, YOIDO-DONG, YOUNGDUNGPO-GU, SEOUL, 150-721, REPUBLIC OF KOREA
Inventors
1. SHIN HYUN-JONG
102-1807, JUNGHEUNG APT., 331-93, JINWOL-DONG, NAM-GU, GWANGIU METROPOLITAN CITY 503-330 KOREA
2. CHOI BYUNG-YUI
NA-203, LG COMPANY'S HOUSING, 1, SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO, 520-130, REPUBLIC OF KOREA
3. YOO YEON-SHICK
NA-106, LG COMPANY'S HOUSING, SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO, 520-130, REPUBLIC OF KOREA
4. CHO YOUNG-JIN
#304, LG CHEMISTRY DORMITORY, 1, SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO 520-130, REPUBLIC OF KOREA
Specification
[DESCRIPTION]
[Invention Title]
MULTI-METAL OXIDE CATALYST AND METHOD FOR PRODUCING
(METH)ACRYLIC ACID BY USING THE SAME
[Technical Field]
The present invention relates to a Mo-Bi-Nb based composite metal oxide(multi-metal
oxide), and a method for producing (meth)acrylic acid from propylene or the like by using the
Mo-Bi-Nb based composite metal oxide as a catalyst. Further, the present invention relates to
a method for producing (meth)acrylic acid from propylene or the like by an one-step catalyst
reaction.
This application claims priority from Korea Patent Application No. 10-2006-71061 filed
on July 27, 2006 in the KIPO, the disclosure of which is incorporated herein by reference in its
entirety.
[Background Art]
A process for producing an unsaturated fatty acid from olefin by way of an unsaturated
aldehyde is a typical process of gas-phase catalytic oxidation.
Particular examples thereof include a process of producing (meth)acrylic acid from a
staring material such as propylene, propane, isobutylene, t-butyl alcohol or methyl-t-butyl ether
(referred to as 'propylene or the like', hereinafter) by way of corresponding (meth)acrolein.
In this connection, in the first step of partially oxidizing olefins to unsaturated aldehyde,
1
composite metal oxides containing molybdenum and bismuth are generally used as a catalyst.
In the second step of partially oxidizing the unsaturated aldehyde, which is a main product of the
first step, to unsaturated fatty acid, composite metal oxides containing molybdenum and
vanadium are used as a catalyst.
More particularly, in the first step, propylene or the like is oxidized by oxygen, inert gas
for dilution, water steam and a certain amount of a catalyst, so as to produce (meth)acrolein as a
main product. Then, in the second step, the (meth) acrolein is oxidized by oxygen, inert gas for
dilution, water steam and a certain amount of a catalyst, so as to produce (meth)acrylic acid.
The catalyst used in the first step is a Mo-Bi based multinary metal oxide, which oxidizes
propylene or the like to produce (meth)acrolein as a main product. Also, some (meth)acrolein
is continuously oxidized on the same catalyst to partially produce (meth)acrylic acid. The
catalyst used in the second step is a Mo-V based multinary metal oxide, which mainly oxidizes
(meth)acrolein of the mixed gas containing the (meth)acrolein produced from the first step to
produce (meth)acrylic acid as a main product.
A reactor for performing the aforementioned process is provided either in such a
manner that both the two-steps can be performed in one system, or in such a manner that the two
steps can be performed in different systems.
As mentioned above, the first-step catalyst involved in gas-phase partial oxidation using
propylene or the like as a starting material is the Mo-Bi based multi-metal oxide, with which
(meth)acrolein is produced as a main product and 10% or less of (meth)acrylic acid is produced.
2
As disclosed in JP-A-8-3093, a conventional first-step catalyst is a composite oxide
represented by the formula of Moa-Bib-Fec-Ad-Be-Cf Dg-Ox (wherein Mo, Bi and Fe represent
molybdenum, bismuth and iron, respectively; A is nickel and/or cobalt; B is at least one element
selected from the group consisting of manganese, zinc, calcium, magnesium, tin and lead; C is at
least one element selected from the group consisting of phosphorus, boron, arsenic, Group 6B
elements in the Periodic Table, tungsten, antimony and silicon; D is at least one element selected
from the group consisting of potassium, rubidium, cesium and thallium; when a=12, 0
Preparation Example 1: Catalyst 1
2500 ml of distilled water was heated and stirred at 70 to 85 °C and 1000 g of
ammonium molybdate was dissolved therein to form a solution 1. Then, 274 g of bismuth
nitrate, 228 g of ferrous nitrate and 2.3 g of potassium nitrate were added to 400 ml of distilled
water, the materials were mixed thoroughly, 71 g of nitric acid was added thereto, and the
materials were dissolved sufficiently to form a solution 2. 686 g of cobalt nitrate was dissolved
in 200 ml of distilled water, so as to form a solution 3. After mixing the solution 2 with the
solution 3, the mixed solution was further mixed with the solution 1 while the temperature was
maintained at 40 to 60 °C, so as to provide a catalyst suspension.
14
The catalyst suspension was dried and the obtained cake-shaped solid was pulverized
into a size of 150 μm or less. The resultant catalyst powder was mixed with a predetermined
amount of water for 2 hours, and formed into a cylindrical shape. The catalyst was formed to
have a diameter of 5.0 mm and a height of 5.0 mm, and calcined at 5001) for 5 hours under the
air, resulting in a catalyst 1. The produced catalyst had the elemental composition of except
oxygen. The resulting catalyst had the following elemental composition except oxygen:
Mo12 Bi1..2 Fe1..2 CO5 K0.05
Preparation Example 2: Catalyst 2
Catalyst 2 was provided in the same manner as described in Preparation Example 1,
except that 64 g of niobium chloride were further added to form a solution 1. The resulting
catalyst had the following elemental composition except oxygen:
Mo12 Nb0.5 Bi1..2 Fe1..2 C05 K0.05
Preparation Example 3: Catalyst 3
Catalyst 3 was provided in the same manner as described in Preparation Example 1,
except that 64 g of niobium chloride were further added to form a solution 1 and the molded
catalyst was allowed to have a diameter of 7 mm and a height of 7 mm. The resulting catalyst
had the following elemental composition except oxygen:
Mo12 Nb0.5 Bi1..2 Fe1..2 C05 K0.05
Preparation Example 4: Catalyst 4
Catalyst 4 was provided in the same manner as described in Preparation Example 1,
15
except that 32 g of niobium chloride were further added to form a solution 1. The resulting
catalyst had the following elemental composition except oxygen:
Mo12 Nb0.5 Bi1..2 Fe1..2 C05 K0.05
Preparation Example 5: Catalyst 5
Catalyst 5 was provided in the same manner as described in Preparation Example 1,
except that 32 g of niobium chloride were further added to form a solution 1 and the molded
catalyst was allowed to have a diameter of 7 mm and a height of 7 mm. The resulting catalyst
had the following elemental composition except oxygen:
Mo12 Nb0.5 Bi1..2 Fe1..2 C05 K0.05
To a 3 m stainless steel reactor having an inner diameter of 1 inch and heated with
molten nitrate salt, alumina silica was packed to a height of 150 mm as an inert material, and
any one or a mixture of Catalysts 1 to 5 prepared in Catalyst Preparation Examples 1 to 5 shown
in Table 1 was packed to have a height of 2800 mm, from the inlet of the reaction gas toward the
outlet.
The oxidation was performed by introducing feed gas containing 7 vol% of propylene,
13 vol% of oxygen, 12 vol% of water steam, and 68 vol% of inert gas onto the catalyst with a
space velocity of 1500 hr-1 (STP), at a reaction temperature of 320 "C under a reaction pressure
of 0.7 arm.
16
In Tables 1, conversion ratio of a reactant and yield are calculated, based on the
following Mathematical Formulae 1 and 2.
[Mathematical Formula 1]
Conversion ratio of propylene (%) = [(mole number of reacted propylene)/(mole
number of supplied propylene)] x 100
[Mathematical Formula 2]
Yield (%) of acrylic acid = [(mole number of produced acrylic acid)/(mole number of
supplied propylene)] x 100
The experimental results of the Examples and Comparative Example are shown in the
following Table 1.
[Table 1]
Section
Comparative 1
Example 1
Example 2
Example 3
Catalyst packed
Catalyst 1 (2800mm)
Catalyst 2 (2800mm)
Catalyst 3 (800mm)
+ Catalyst 2 (2000mm)
Catalyst 5 (800mm)
+ Catalyst 4 (2000mm)
Conversion ratio of
propylene (%)
3201
98.67
92.21
91.44
93.87
Yield (mole %) of
acrylic acid
9.51
67.40
72.65
76.84
We claim:
[Claim 1]
A reactor for producing (meth)acrylic acid using one or more reactant selected from
the group consisting of propylene, propane, isobutylene, t-butyl alcohol and methyl-t-butyl
5 ether, the reactor comprising an inlet, an outlet, and a reaction zone,
wherein the reaction zone includes a catalyst of a Mo-Bi-Nb based composite metal
oxide, the catalyst being represented by the following Formula 1:
[Formula 1]
MOa Bib Nbc Ad Be Cf Dg Eh F| Oj
10 wherein Mo represents molybdenum, Bi represents bismuth, and Nb represents
niobium;
A is one or more element selected from the group consisting of W, Sb, As, P, Sn and
Pb;
B is one or more element selected from the group consisting of Fe, Zn, Cr, Mn, Cu, Pd,
15 Ag and Ru;
C is one or more element selected from the group consisting of Co, Cd, Ta, Pt and Ni;
D is one or more element selected from the group consisting of Si, Al, Zr, V and Ce;
E is one or more element selected from the group consisting of Se, Ga, Ti, Ge, Rh
and Au;
20 F is one or more element selected from the group consisting of Na, K, Li, Rb, Cs, Ca,
Mg, Sr, Ba and MgO;
each of a, b, c, d, e, f, g, h, i, and j represents the atomic ratio of each element; and
when a=12, b is 0.01 to 20, c is 0.001 to 20, d is 0 to 15, e is 0 to 20, f is 0 to 20, g is 0
to 10, h is 0 to 10, i is 0 to 10, and j is a value defined by the oxidation state of each of the
25 above elements, proviso that g is zero and Te is not included.
[Claim 2]
The reactor as claim in claim 1, wherein the reactor is a shell and tube type reactor,
wherein the shell and tube type reactor further comprises a tube that includes the
30 reaction zone, and
wherein the reaction zone of the tube is packed with the Mo-Bi-Nb based composite
metal oxide catalyst.
18
10
'^}M
[Claim 3]
The reactor - as claim in claim 2, wherein the reaction zone of the tube includes two
or more catalyst beds based on the Mo-Bi-Nb based composite metal oxide.
[Claim 4]
The reactor as claim in claim 3, wherein the reaction zone of the tube includes two or
more of catalyst beds having different catalytic activities in order to increase the catalytic
activity of the catalyst bed from the inlet, in which the reactants are introduced, to the outlet,
in which the reaction products are outputted, along its tubular axis.
[Claim 5]
The reactor as claim in claim 2, wherein the reaction zone of the tube includes two or
more different catalyst beds so that the particle size of the catalyst in the catalyst beds
packed with Mo-Bi-Nb based composite metal oxide decreases from the inlet, in which the
15 reactants are introduced, to the outlet, in which the reaction products are outputted, along
its tubular axis.
[Claim 6]
The reactor as claim in claim 4, wherein the reaction zone of the tube includes two or
20 more different catalyst beds packed with Mo-Bi-Nb based composite metal oxide and the
different molar ratios of Nb to Mo ([Nb]/[Mo]) and the catalytic activity of each of the
catalyst beds increases from the inlet, in which the reactants are introduced, to the outlet,
in which the reaction products are outputted, along its tubular axis.
25 [Claim 7]
The reactor as claim in claim 1, wherein the reactor is a fixed-bed reactor, a fluidizedbed
reactor or a moving-bed reactor.
[Claim 8]
30 The reactor as claim in claim 1, wherein the catalyst has a yield of 60 mol% or more
19
(
when used as a single catalyst.
[Claim 9]
The reactor as claim in claim 7,
wherein the reactor is a fluidized-bed reactor, and
wherein a mixture of solid catalyst and reaction gas moves through the inlet to the
reaction zone to the reaction zone, and after reaction, non-reactants, products and the
catalyst move though the outlet in a mixed state.