Abstract:
Disclosed are a Mo-Bi-Nb-Te based composite metal oxide; and a process for producing (meth)acrylic acid from at least one reaction material selected from the group consisting of propylene, propane, isobutylene, t-butyl alcohol and methyl-t-butyl ether, wherein the Mo-Bi-Nb-Te based composite metal oxide is used as a catalyst. Also, disclosed is a process for producing (meth)acrylic acid comprising a first step of producing (meth)acrolein as a main product from at least one reaction material selected from the group consisting of propylene, propane, isobutylene, t-butyl alcohol and methyl-t-butyl ether, and a second step of producing (meth)acrylic acid from the (meth)acrolein, wherein yield of (meth)acrylic acid in the product of the first st...
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Notices, Deadlines & Correspondence
Technical Field
The present invention relates to a Mo-Bi-Nb-Te
based composite metal oxide, and a process for producing
(meth) acrylic acid from propylene or the like by using
the Mo-Bi-Nb-Te, based composite metal oxide as a
catalyst Also, the present invention relates to a
process for producing (meth)acrylic acid comprising a
first step of producing (meth)acrolein as a main product
from propylene or the like, and a second step of
producing (meth)acrylic acid from the (meth)acrolein,
wherein the yield of (meth)acrylic acid in the product
of the first step is 20 mole% or higher
Background Art
A process for producing an unsaturated fatty acid
from an olefin by way of an unsaturated aldehyde is a
typical process of catalytic vapor phase oxidation To
perform partial oxidation of olefins, composite oxides
containing molybdenum and bismuth, molybdenum and
vanadium, or mixtures thereof are used as catalysts
Particular examples of such catalytic vapor phase
oxidation include a process of producing (meth)acryliu
acid by the oxidation of propylene or isobutylene by way
of (meth)acrolein, a process of producing phthalic
anhydride by the oxidation of naphthalene or
orthoxylene, and a process of producing maleic anhydride
by the partial oxidation of benzene, butylene or
butadiene
Generally, (meth)acrylic acid, a final product, is
produced from at least one reaction material selected
from the group consisting of propylene, propane,
isobutylene, t-butyl alcohol or methyl-t-butyl ether
(referred to as 'propylene or the like' , hereinafter) by
a two-step process of vapor phase catalytic partial
oxidation 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
mam product Also, some 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 in 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 hereinbefore, tne first-step catalyst
involved in vapor phase partial oxidation using
propylene or the like as a starting material is a
multinary metal oxide, with which (meth)acrolein is
produced as a main product and at most 10% of
(meth)acrylic acid is produced
As disclosed in Japanese Laid-Open Patent No
Hei8-3093, a conventional first-step catalyst is a
composite oxide represented by the formula of Moa-B1b-
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, each of a, b, c, e, f and
g is a number satisfying the conditions of 0
Preparation Example 1 Catalyst 1
First, 2500 ml of distilled water was heated and
stirred at 70°C~ 85°C and lOOOg of ammonium molybdate was
added thereto to form solution (1) Next, 274g of
bismuth nitrate, 228g of ferrous nitrate and 2 3g of
potassium nitrate were added~ to 400ml of distilled
water, the materials were mixed thoroughly, 71g of
nitric acid was added thereto, and the materials were
dissolved sufficiently to form solution (2) To 200ml of
distilled water, 686g of cobalt nitrate was dissolved to
form solution (3) After mixing solution (2) with
solution (3) , the mixed solution was further mixed with
solution (1) while maintaining the temperature at
40- 60°C to provide a catalyst suspension
The catalyst suspension was dried to produce
M012B11 2Fei 2C05K0 05 and the catalyst was pulverized into a
size of 150^m or less The resultant catalyst powder was
mixed for 2 hours and formed into a cylindrical shape
The catalyst was formed to have an outer diameter of
4 0-8 0mm, and calcined at 500°C for 5 hours under the
aj.r, and then the catalytic activity was verified
Preparation Example 2 Catalyst 2
Catalyst 2 was provided in the same manner as
described in Preparation Example 1, except that 63g of
niobium chloride and 150g of tellurium chloride were
further added to form solution (1) The catalyst had the
elemental composition of M012ND0 5TeiBii 2Fei 2C05K0 05 except
oxygen
Preparation Example 3 Catalyst 3
Catalyst 3 was provided in the same manner as
described in Preparation Example 1, except that 127g of
niobium chloride and 150g of tellurium nitrate were
further added to form solution (1) The catalyst had the
elemental composition of Moi2Nbi 0Tei 0Bii 2Fei 2Co4 5K0 05
except oxygen
Preparation Example 4 Catalyst 4
Catalyst 4 was provided in the same manner as
described in Preparation Example 1, except that 63g of
niobium chloride and 75g of tellurium chloride were
further added to form solution (1) The catalyst had the
elemental composition of Moi2Nbo sTeiBii 2?ei 2C04 5K0 05
except oxygen
Preparation Example 5 Catalyst 5
First, 2000 ml of distilled water was heated and
stirred at 100°C and 246g of ammonium tungstate, lOOOg of
ammonium molybdate and 220g of ammonium vanadate were
dissolved therein to form solution (1) Next, 228g of
copper nitrate and 4 9g of strontium nitrate were added
to 500ml of distilled water, and the materials were
mixed thoroughly to form solution (2) Solution (1) was
mixed with solution (2) to provide a suspension The
suspension was treated by using a homogenizer for at
least 30 minutes and was coated- on spherical- carriers
having an outer diameter of 4 0-8 0mm by using a spray
nozzle to an amount of 20- 30 wt% as expressed by the
catalytically active component present in the
suspension The coated catalyst was dried at 120°C
sufficiently and calcined at 400°C for at least 5 hours
to provide spherical catalyst particles having a final
outer diameter of 5mm{±0 2)
The catalyst had the elemental composition of
M012W2 0V4 0CU2 oSr0 5 except oxygen
Experiment Catalyst Packing and Catalytic
Activity Test>
To a 3m stainless steel reactor having an inner
diameter of 1 inch and heated with molten nitrate salt,
alumina silica was packed to a height of 150mm as an
inert material, and any one of Catalysts 1~ 4 was packed
to a height of 2800mm as the first-step catalyst, from
the inlet of the reaction gas toward the outlet
Then, alumina silica was packed to a height of
150mm as an inert material and Catalyst 5 was packed to
a height of 2900mm as the second-step catalyst
Propylene was subjected to vapor phase oxidation by
using the reactor to produce acrolein and acrylic acid
The first-step oxidation was performed by introducing
feed gas containing 7 vol% of propylene, 13 vol% of
molecular oxygen, 8 vol% of water steam and 72 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 atm The second-step
oxidation was performed at a reaction temperature of
276°C, under a reaction pressure of 0 1~ 3kg/cm2G
In the following Tables 1 and 2, conversion ratio
of a reaction material, selectivity and yield are
calculated based on the following Mathematical Formulae
1~ 7
[ Mathematical Formula 1]
first-step propylene conversion ratio(%) = [ moles
of reacted propylene/moles of supplied propylene] X 100
[ Mathematical Formula 2]
yield(%) of acrolein in the first step = [moles of
produced acrolein/moles of supplied propylene] X 100
[ Mathematical Formula 3]
yield(%) of acrylic acid in the first step= [moles
of produced acrylic acid/moles of supplied propylene] X
100
[ Mathematical Formula 4]
selectivity(%) of acrolein + acrylic acid in the
first step = [ moles of produced acrolein and acrylic
acid/moles of reacted propylene] X 100
[ Mathematical formula 5]
second-step acrolein conversion ratio(%) = [moles
of reacted acrolein/moles of supplied acrolein] X 100
[ Mathematical Formula 6]
yield(%) of acrylic acid in the second step=
[ moles of produced acrylic acid/moles of supplied
acrolein] X 100
[ Mathematical Formula 7]
selectivity(%) of acrylic acid in the second step
= [ moles of produced acrylic acid/moles of reacted
acarolein] X 100
The experimental results of the Examples according
to the present invention and Comparative Example are
shown in the following Table 1 (first-step oxidation)
and Table 2 {second-step oxidation)
Industrial Applicability
As can be seen from the foregoing, when the Mo-Bi-
Nb-Te based composite metal oxide according to the
present invention is used as the first-step catalyst in
the production of (meth)acrylic acid from propylene or
the like, yield and/or selectivity of (meth)acrylic acid
increases in the first-step reaction product, and thus
(meth)acrolein load decreases in the second-step to such
a degree that (meth*) acrolein conversion ratio can reach
98- 100%
While this invention has been described in
connection with what is presently considered to be the
most practical and preferred embodiment, it is to be
understood that the invention is not limited to the
disclosed embodiment and the drawings On the contrary.
it is intended to cover various modifications and
variations within the spirit and scope of the appended
claims
WE CLAIM
1 A process for producing (meth) acrylic acid comprising a first step of producing (meth)
acrolein as a main product from at least one reaction material selected from the group consisting of
propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether, and a second step of producing
(meth) acrylic acid from the (meth) acrolein, wherein yield of (meth)acrylic acid in the product of
the first step is 20 mole % or higher, wherein a Mo-Bi-Nb-Te based composite metal oxide is used
as a catalyst of the first step and the composite metal oxide is represented by the following
Formula 1
[Formula 1 ]
MOaB1bNbcTedFefCogKJOk
Wherein Mo represents molybdenum, Bi represents bismuth, Nb represents niobium, Te represents
tellurium, Fe represents iron, Co represents cobalt, K represents potassium, and O represents
oxygen,
each of a, b, c, d, f, g, j and k represents the atomic ratio of each element,
wherein when a= 12, b is 0 01-20, c is 0 001-20, d is 0 001-20, f is 1 2, g is 4 5 or 5, J is 0 05, and
k is a number defined by the oxidation state of each of the above elements
2 The process as claimed in claim 1, wherein the first-step reaction product includes (meth)
acrolein and (meth) acrylic acid in a molar ratio ((meth)acrolein (meth) acrylic acid) of 8 2-7 3
3 The process as claimed in claim 1, wherein conversion ratio of (meth) acrolein in the second
step is 98% - 100%
4 The process as claimed in claim 1, wherein the reaction material introduced into the first
step comprises at least one reaction material selected from the group consisting of propylene,
isobutylene, t-butyl alcohol and methyl-t-butyl ether in a concentration of 7-10 vol %
ABSTRACT
PROCESS FOR PRODUCTION OF (METH)
ACRYLIC ACID
The invention is for a process for producing (meth)acrylic acid comprising a
first step of producing (meth)acrolein as a main product from at least one reaction
material selected from the group consisting of propylene, isobutylene, t-butyl alcohol
and methyl-t-butyl ether, and a second step of producing (meth)acrylic acid from the
(meth)acrolein, wherein yield of (meth)acrylic acid in the product of the first step is 20
mole % or higher, wherein a Mo—B1—Nb—Te based composite metal oxide is used as
a catalyst of the first step and the composite metal oxide is represented by the following
Formula 1
[Formula 1]
MOaB1bNbcTedFefCOgKJOI
Wherein Mo represents molybdenum, B1 represents bismuth, Nb represents niobium, Te
represents tellurium, Fe represents iron, Co represents cobalt, K represents potassium,
and 0 represents oxygen,
each of a, b, c, d, f, g, j and k represents the atomic ratio of each element,
wherein when a=12, b is 0 01-20, c is 0 001-20, d is 0 001-20, f is 1 2 g is 4 5 or 5, j is
0 05, and k is a number defined by the oxidation state of each of the above elements
Documents
Orders
Section
Controller
Decision Date
Application Documents
#
Name
Date
1
470-kolnp-2008-form 18.pdf
2011-10-06
2
470-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf
2011-10-06
3
470-KOLNP-2008-ASSIGNMENT 1.1.pdf
2011-10-06
4
00470-kolnp-2008-international publication.pdf
2011-10-06
5
00470-kolnp-2008-gpa.pdf
2011-10-06
6
00470-kolnp-2008-form 5.pdf
2011-10-06
7
00470-kolnp-2008-form 3.pdf
2011-10-06
8
00470-kolnp-2008-form 1.pdf
2011-10-06
9
00470-kolnp-2008-description complete.pdf
2011-10-06
10
00470-kolnp-2008-correspondence others.pdf
2011-10-06
11
00470-kolnp-2008-claims 1.1.pdf
2011-10-06
12
00470-kolnp-2008-claims 1.0.pdf
2011-10-06
13
00470-kolnp-2008-abstract.pdf
2011-10-06
14
00470-KOLNP-2008-FORM 13.pdf
2012-02-23
15
470-KOLNP-2008-(18-02-2013)-PETITION UNDER RULE 137.pdf
2013-02-18
16
470-KOLNP-2008-(18-02-2013)-PETITION UNDER RULE 137-1.pdf