EP1358147A1 - Improved method for the manufacture of acrylic acid - Google Patents

Improved method for the manufacture of acrylic acid

Info

Publication number
EP1358147A1
EP1358147A1 EP01905424A EP01905424A EP1358147A1 EP 1358147 A1 EP1358147 A1 EP 1358147A1 EP 01905424 A EP01905424 A EP 01905424A EP 01905424 A EP01905424 A EP 01905424A EP 1358147 A1 EP1358147 A1 EP 1358147A1
Authority
EP
European Patent Office
Prior art keywords
acrylic acid
catalyst
acrolein
reaction zone
manufacture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01905424A
Other languages
German (de)
French (fr)
Inventor
Dev D. Suresh
Christos Paparizos
Patrick E. Mosier
Ying Wu
Maria Strada Friedrich
Michael J. Seely
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos USA LLC
Original Assignee
Standard Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Standard Oil Co filed Critical Standard Oil Co
Publication of EP1358147A1 publication Critical patent/EP1358147A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J35/19—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

Definitions

  • the present invention is directed to an improved process for the
  • acrylic acid is produced by a two-step
  • the catalyst was specifically disclosed as containing a mixed metal oxide of iron, molybdenum and bismuth promoted with various metals and
  • step of the two-step process for the manufacture of acrylic acid results in unexpected high yield of acrylic acid during the first step of the process.
  • present invention comprises reacting propylene and oxygen (preferably in the
  • A one or more of Li, Na, K, Rb and Cs
  • B one or more of Mg, Sr, Mn, Ni, Co and Zn
  • an elevated temperature e.g. 200° to 600°C
  • A is selected to be
  • Hthium one or more of Hthium, sodium, potassium and cesium, especially preferred being
  • B is selected from the group
  • C is selected from the group comprising cerium, chromium, antimony, phosphorus, germanium, tungsten, or
  • a may range from about .05 to .9, especially preferred being above 0.1 to 0.7.
  • c, d and f may range from about 0.05 to 4, especially preferred being 0.1 to 3.
  • a further preferred embodiment of the present invention comprises recovering the acryhc acid and acrolein from the first reaction zone, introducing
  • acrolein and oxygen into a second reaction zone having a second catalyst to react the acrolein and oxygen at an elevated temperature to produce acrylic acid, and recovering the acryhc acid from the second reaction zone.
  • Any suitable acrolein to acryhc acid catalyst may be used in this second step.
  • typical second stage catalysts e.g., 62% Sb3Sn3N3W ⁇ .2Moi2 ⁇ x • 38% SiO 2 ) as
  • the first reaction from propylene to acrylic acid and acrolein takes place in a fluid bed reactor and the second reaction from acrolein to acrylic acid takes place in a fixed
  • the catalyst of the present invention can be used either supported or unsupported.
  • the catalyst is supported on silica, alumina or zirconium or mixtures thereof, especially preferred being silica.
  • the catalysts of the present invention may be prepared by any of the following
  • the catalyst may be manufactured by co-precipitating the various ingredients.
  • the co-precipitating mass may then be dried and ground to an appropriate size.
  • the co-precipitated material may be slurried and spray dried in accordance with conventional techniques.
  • the catalyst may be manufactured by co-precipitating the various ingredients.
  • the co-precipitating mass may then be dried and ground to an appropriate size.
  • the co-precipitated material may be slurried and spray dried in accordance with conventional techniques.
  • the catalyst may be manufactured by co-precipitating the various ingredients.
  • the co-precipitating mass may then be dried and ground to an appropriate size.
  • the co-precipitated material may be slurried and spray dried in accordance with conventional techniques.
  • the catalyst components may be mixed with a support in the form. of the slurry followed by drying or they may be impregnated on silica or other
  • the A component of the catalyst may be introduced into the
  • catalyst as an oxide or as a salt which upon calcination will yield the oxide.
  • salts such as nitrates which are readily available and easily soluble are used as the means of incorporating the A element into the catalyst.
  • Bismuth may be introduced into the catalyst as an oxide or as a salt which upon calcination will yield the oxide.
  • the water soluble salts which are
  • An especially preferred source for introducing bismuth is bismuth nitrate which has been dissolved in a solution of nitric acid.
  • water soluble salts are preferred for the ease with which they
  • Cobalt, nickel and magnesium may also be introduced into the catalyst using nitrate salts. However, magnesium may also be introduced into the catalyst as an insoluble carbonate or hydroxide which upon heat treating results
  • the molybdenum component of the catalyst may be introduced from any molybdenum oxide such as dioxide, trioxide, pentoxide or heptaoxide. However, it is preferred that a hydrolizable or decomposable molybdenum salt be utilized as the source of the molybdenum.
  • a hydrolizable or decomposable molybdenum salt be utilized as the source of the molybdenum. The most preferred starting material is
  • Phosphorus may be introduced in the catalyst as an alkaline metal salt
  • the present invention can be added via pre-formation of calcium molybdate or by impregnation or by other means known in the art. (Usually added as Ca-nitrate, along with the other nitrates.)
  • the present invention is directed to a process for the production of
  • A one or more of Li, Na, K, Rb and Cs
  • B one or more of Mg, Sr, Mn, Ni, Co and Zn
  • reaction takes place
  • the catalysts of the present invention may be prepared by mixing an
  • the catalyst may be spray-dried at a temperature of between 110°C to 350°C.
  • the denitrification temperature may
  • introducing at least the acrolein and oxygen preferably, air is the source for the
  • catalysts useful in the second reaction zone include Mo 9 V 2 W ⁇ Cu ⁇ Sn 0 .4 ⁇ x ; Mo ⁇ oW ⁇ V 3 Sb 2 Cu ⁇ Nb2 ⁇ x ; M012V3W1.2Cu2Tio.5Ox;
  • catalysts are supported on an inert support such as alumina, zirconia or silica,
  • the supported catalyst comprises 70 to 75 wt% active

Abstract

A process for the manufacture of acrylic acid comprising reacting propylene and oxygen (preferably in the form of air) in a reaction zone having a catalyst characterized by the following formula: AaBbCcCadFeeBifMo12=Ox, where A = one or more of Li, Na, K, Rb and Cs; B = one or more of Mg, Sr, Mn, Ni, Co and Zn; C = one or more of Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and; a = 0.01 to 1.0; b and e = 1.0 - 10; c = 0 to 5.0, preferably 0.05 to 5.0, especially preferred being 0.05 to 4.0, and x is a number determined by the valence requirements of the other elements present; at an elevated temperature to produce acrylic acid and acrolein.

Description

SPECIFICATION
IMPROVED METHOD FOR THE MANUFACTURE
OF ACRYLIC ACID
BACKGROUND OF THE INVENTION
The present invention is directed to an improved process for the
manufacture of acrylic acid. Presently, acrylic acid is produced by a two-step
process. Propylene is first oxidized to acrolein over a mixed metal oxide catalyst
comprising iron, bismuth and molybdenum promoted with suitable elements, and the acrolein is further oxidized to acrylic acid over a second catalyst in a
separate reactor. Typically, catalysts containing oxides of iron, bismuth and
molybdenum promoted with suitable elements are readily available for the
selective oxidation of the propylene to acrolein (i.e. this first step in the two-step process in the manufacture of acrylic acid). Examples of suitable types of catalysts for this first step can be found in U.S. Patent 4,162,234 and 4,280,929
assigned to the assignee of the present application.
In the second step of the two-step process acrolein is oxidized over the
second catalyst to acrylic acid. It is always the case that the selectivity of the acrolein to acrylic acid is below 100%. However, the acrylic acid that is formed in the first step of the two-step process passes through the second reactor with no
decomposition. Therefore, it is advantageous to use catalysts that produce substantially larger amounts of acrylic acid during the oxidation of the propylene
to acrolein in the first reactor, thereby getting higher yields of acrylic acid in the
two-step process.
In related patent application U.S. Serial No. 08/923,878 filed September 2, 1997, and assigned to the assignee of the present invention, there
is a disclosure of a novel catalyst useful in the manufacture of acrylonitrile and
hydrogen cyanide. The catalyst was specifically disclosed as containing a mixed metal oxide of iron, molybdenum and bismuth promoted with various metals and
useful in the manufacture of acrylonitrile with substantially higher yields of co-
product hydrogen cyanide. It is the discovery of the instant application that the
catalyst of co-pending application 08/923,878 can not only be used in the first
step of the two-step process for the manufacture of acrylic acid, but results in unexpected high yield of acrylic acid during the first step of the process. This
high yield of acrylic acid in the first step leads to a higher yield of acrylic acid overall being achieved in the two-step process. SUMMARY OF THE INVENTION
It is a primary object of the present invention to provide a novel process
for the production of acrylic acid and selected oxidation of propylene to acrolein.
Additional objects and advantages of the invention will be set forth in part in the description which follows and in part will be obvious from the
description, or may be learned by the practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended
claims.
To achieve the foregoing objects and in accordance with the purpose of
the present invention as embodied and described herein, the process of the
present invention comprises reacting propylene and oxygen (preferably in the
form of an oxygen-containing gas such as air) in a reaction zone having a
catalyst characterized by the following formula:
AaBbCcCadFeeBifMo12Ox
where A = one or more of Li, Na, K, Rb and Cs
B = one or more of Mg, Sr, Mn, Ni, Co and Zn
C = one or more of Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and a = 0.01 to 1.0; b and e = 1.0 - 10 c = 0 to 5.0, preferably 0.05 to 5.0, especially preferred being
0.05 to 4.0 d and f = 0.05 to 5.0,-and x is a number determined by the
valence requirements of the other elements present;
at an elevated temperature (e.g. 200° to 600°C) to produce acrylic acid and acrolein.
In the preferred embodiment of the present invention, A is selected to be
one or more of Hthium, sodium, potassium and cesium, especially preferred being
cesium and potassium.
In another preferred embodiment, B is selected from the group
consisting of magnesium, manganese, nickel and cobalt, or mixtures thereof. In still another preferred embodiment, C is selected from the group comprising cerium, chromium, antimony, phosphorus, germanium, tungsten, or
mixtures thereof, especially preferred being cerium, chromium, phosphorus, and
germanium.
In still another preferred embodiment of the present invention, a may range from about .05 to .9, especially preferred being above 0.1 to 0.7.
In a further preferred embodiment of the present invention, b and e
may range from about 1 to 10. In still a further preferred embodiment of the
present invention, c, d and f may range from about 0.05 to 4, especially preferred being 0.1 to 3. A further preferred embodiment of the present invention comprises recovering the acryhc acid and acrolein from the first reaction zone, introducing
at least acrolein and oxygen into a second reaction zone having a second catalyst to react the acrolein and oxygen at an elevated temperature to produce acrylic acid, and recovering the acryhc acid from the second reaction zone. Any suitable acrolein to acryhc acid catalyst may be used in this second step. For example, typical second stage catalysts (e.g., 62% Sb3Sn3N3Wι.2Moi2θx • 38% SiO2) as
described in U.S. Patent 3,840,595, herein incorporated by reference, are
suitable in the practice of the present invention.
In another preferred embodiment of the present invention, the first reaction from propylene to acrylic acid and acrolein takes place in a fluid bed reactor and the second reaction from acrolein to acrylic acid takes place in a fixed
bed reactor.
The catalyst of the present invention can be used either supported or unsupported. Preferably the catalyst is supported on silica, alumina or zirconium or mixtures thereof, especially preferred being silica.
Detailed Description of the Invention
The catalysts of the present invention may be prepared by any of the
numerous methods of catalyst preparation which are known to those of skill in
the art. For example, the catalyst may be manufactured by co-precipitating the various ingredients. The co-precipitating mass may then be dried and ground to an appropriate size. Alternatively, the co-precipitated material may be slurried and spray dried in accordance with conventional techniques. The catalyst may
be extruded as pellets or formed into spears in oil as is well known in the art.
Alternatively, the catalyst components may be mixed with a support in the form. of the slurry followed by drying or they may be impregnated on silica or other
supports. For particular procedures for manufacturing the catalyst, see U.S.
Patents 5,093,299; 4,863,891 and 4,766,232 assigned to the assignee of the
present invention, herein incorporated by reference.
Typically, the A component of the catalyst may be introduced into the
catalyst as an oxide or as a salt which upon calcination will yield the oxide.
Preferably, salts such as nitrates which are readily available and easily soluble are used as the means of incorporating the A element into the catalyst.
Bismuth may be introduced into the catalyst as an oxide or as a salt which upon calcination will yield the oxide. The water soluble salts which are
easily dispersed but form stable oxides upon heat treating are preferred. An especially preferred source for introducing bismuth is bismuth nitrate which has been dissolved in a solution of nitric acid.
To introduce the iron component into the catalyst, one may use any
compound of iron which, upon calcination will result in the oxides. As with the
other elements, water soluble salts are preferred for the ease with which they
may be uniformly dispersed within the catalyst. Most preferred is ferric nitrate. Cobalt, nickel and magnesium may also be introduced into the catalyst using nitrate salts. However, magnesium may also be introduced into the catalyst as an insoluble carbonate or hydroxide which upon heat treating results
in an oxide.
The molybdenum component of the catalyst may be introduced from any molybdenum oxide such as dioxide, trioxide, pentoxide or heptaoxide. However, it is preferred that a hydrolizable or decomposable molybdenum salt be utilized as the source of the molybdenum. The most preferred starting material is
ammonium heptamolybdate.
Phosphorus may be introduced in the catalyst as an alkaline metal salt
or alkaline earth metal salt or the ammonium salt but is preferably introduced as phosphoric acid. Calcium which is an essential ingredient in the catalyst of
the present invention can be added via pre-formation of calcium molybdate or by impregnation or by other means known in the art. (Usually added as Ca-nitrate, along with the other nitrates.)
The present invention is directed to a process for the production of
acrylic acid during the oxidation of propylene to acrolein comprising reacting oxygen and propylene in a reaction zone in contact with a catalyst characterized by the following empirical formula:
AaBbCoCadFeeBifMoi2θx where A = one or more of Li, Na, K, Rb and Cs
B = one or more of Mg, Sr, Mn, Ni, Co and Zn
C = one or more of Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and a = 0.01 to 1.0; b and e = 1.0 - 10 c = 0 to 5.0, preferably 0.05 to 5.0, especially preferred being
0.05 to 4.0 d and f = 0.05 to 5.0, and x is a number determined by the valence requirements of the other elements present;
to produce acrylic acid and acrolein. Preferably, the reaction takes place
between a temperature of 200° to 500°C, preferably 300° to 400°C.
The catalysts of the present invention may be prepared by mixing an
aqueous solution of ammonium heptamolybdate with a sihca sol, adding a slurry containing the compounds of the other elements to the aqueous solution, drying
the solution, denitrifying and calcining. The catalyst may be spray-dried at a temperature of between 110°C to 350°C. The denitrification temperature may
range from 100°C to 450°C. Finally, calcination takes place at a temperature of
between 400°C to 700°C.
A further preferred embodiment of the present invention comprising
recovering the acrylic acid and acrolein produced in the first reaction zone,
introducing at least the acrolein and oxygen (preferably, air is the source for the
oxygen) into a second reaction zone at an elevated temperature containing a
second catalyst suitable for the conversion of acrolein to acrylic acid to convert
the acrolein to acrylic acid and recovering the acrylic acid from the second
reaction zone. Suitable catalysts for use in the conversion of acrolein to acrylic acid are described in previously cited U.S. Patent 3,840,595, herein incorporated by reference. Specific examples of catalysts useful in the second reaction zone include Mo9V2WιCuιSn0.4θx; MoιoWιV3Sb2CuιNb2θx; M012V3W1.2Cu2Tio.5Ox;
Mo9V2WιCuι.5Sno.4PιOχ; M012V3W1.2Cu2Sno.5Ox and SbsSn3V3Wι.2Moi2θχ. These
catalysts are supported on an inert support such as alumina, zirconia or silica,
preferably silica. Typically, the supported catalyst comprises 70 to 75 wt% active
phase and 25 to 30 wt% inert support.
The following examples of the present invention are set forth below for
illustrative purposes only.
In each of the following examples, the process was performed in a 40 cc
fluid bed reactor at 0.05-0.10 wwh with a feed mixture of 1C3= / 1.7O2 /9.3N2 /
3H2O at a temperature of 360°C and 15 psig.
Table I

Claims

What we claim as our invention is:
1. A process for the manufacture of acrylic acid comprising reacting
propylene and oxygen in a first reaction zone having a first catalyst characterized by the following formula:
AaBbC-CadFeeBifMoι2Ox
where A = one or more of Li, Na, K, Rb and Cs
B = one or more of Mg, Sr, Mn, Ni, Co and Zn
C = one or more of Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W
and a = 0.01 to 1.0; b and e = 1.0 - 10
c = 0 to 5.0
d and f = 0.05 to 5.0, and x is a number determined by the
valence requirements of the other elements present;
at an elevated temperature to produce acrylic acid and acrolein.
2. The process of claim 1 further comprising introducing at least
acrolein from the first reaction zone and oxygen into a second reaction zone
containing a second catalyst to convert the acrolein into acrylic acid.
3. The process of claim 1 wherein A is selected to be one or more of
lithium, sodium, potassium and cesium.
4. The process of claim 3 wherein B is selected from the group
consisting of magnesium, manganese, nickel and cobalt, or mixtures thereof.
5. The process of claim 4 wherein C is selected from the group
consisting of cerium, chromium, phosphorus, and germanium, or mixtures thereof.
6. The process of claim 5 wherein a ranges from about .05 to .9.
7. The process of claim 6 wherein b and e range from about 2 to 9.
8. The process of claim 7 wherein c, d and f range from about 0.1 to
4.
EP01905424A 2001-02-05 2001-02-05 Improved method for the manufacture of acrylic acid Withdrawn EP1358147A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2001/003606 WO2002062741A1 (en) 2001-02-05 2001-02-05 Improved method for the manufacture of acrylic acid

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EP (1) EP1358147A1 (en)
JP (1) JP2004522757A (en)
KR (1) KR100711044B1 (en)
CN (1) CN1216846C (en)
BR (1) BR0116860A (en)
CA (1) CA2437256C (en)
MX (1) MXPA03006957A (en)
WO (1) WO2002062741A1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS584691B2 (en) * 1977-11-07 1983-01-27 宇部興産株式会社 Method for producing methacrolein
US5218146A (en) * 1987-05-27 1993-06-08 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for production of acrylic acid
US5840648A (en) * 1997-09-02 1998-11-24 The Standard Oil Company Catalyst for the manufacture of acrylonitrile and hydrogen cyanide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02062741A1 *

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WO2002062741A1 (en) 2002-08-15
CN1216846C (en) 2005-08-31
CA2437256A1 (en) 2002-08-15
KR20030076655A (en) 2003-09-26
CA2437256C (en) 2009-04-14
MXPA03006957A (en) 2004-05-24
BR0116860A (en) 2004-01-13
JP2004522757A (en) 2004-07-29
CN1489568A (en) 2004-04-14
KR100711044B1 (en) 2007-04-24

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