CA1132124A - Oxidation catalysts - Google Patents
Oxidation catalystsInfo
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- CA1132124A CA1132124A CA306,799A CA306799A CA1132124A CA 1132124 A CA1132124 A CA 1132124A CA 306799 A CA306799 A CA 306799A CA 1132124 A CA1132124 A CA 1132124A
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- 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
- 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
- B01J23/8875—Germanium, tin or lead
-
- 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
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(5027) OXIDATION CATALYSTS
ABSTRACT OF THE DISCLOSURE
Catalysts containing iron, bismuth, molybdenum. and various additional elements exhibit extremely attractive catalytic properties for the oxidation and ammoxidation of various olefins.
ABSTRACT OF THE DISCLOSURE
Catalysts containing iron, bismuth, molybdenum. and various additional elements exhibit extremely attractive catalytic properties for the oxidation and ammoxidation of various olefins.
Description
BACKGROUND OF THE INVENTION
. ~atal~sts for the oxidation, ammoxldation and oxvdeh~dro~enatlon Or olefins are well known. See t f~r example, U.S. 3~642,930 and U. S. 3,414,631. Although these catalysts of the art are very desirable, the ca$alysts 10~ of the present invention have significant advantages over these other ~atalysts~
~ .
., SU~IARY AN3 DE~AIL~D DESCRIP~IO~ O~ THE I~ IO~J
The present lnvention is based on the discovery ~hat certain oxldztion catalysts based on iron, bismuth and ~olybde~um and contalnin~ additiona~ speclfied promoter elements exhiblt excellent catalytic activlty for a variety o~ ole~ln oxidatlon, ammoxldatlon, dehydrogenation and oxydehydrogenatlon reactlons. In particular, lt has been round that speci~ic catalytlc compositions as descrlbed `
~ ~ 3 ~ (5-_7~
below are es~e~i211y suited for use in prcducln~ acr~'-o-nitrile and m~thacrylonitrlle by the amms~ld2tion Or propyl-ene and isobutylene, resDectively. In addition to being excellent am~oxidation ca~alysts for the production of acrylonitrile or methacrylonitrile, these catalysts aiso exhibit excellent catalytic activity for the conversion of olerins having four or more contiguous carbon 2toms to the corresponding dioiefins, and in the oxydehydro~enatior. of ole~ins to diolefins.
l~ In accordance with the present invention, novel catalysts having improved catalytic propert~es are repre-sented by the following empirical formula a~b7~cFe~DeMol2ox wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is ~o, Ni, Zn, Cd, Be, r~, Ca, Sr, Ba, ~a or mixtures thereof;
Z is a two-or-more element system selected from the group consisting o~ ~7e T Sb, Cu + W~
Cu + Sn, Ce + W, Pr + ~n, Sn + r'n, ~'r + t~
W + Sb, Cr ~ Sn, W + Sn, Ge + Sn, Sb + Sn, W ~ P, Sb ~ P, Cr + Cu, Mn + Cu, Sb + Cu, ~n + P or mlxtures thereof, with the proviso that said catalyst is free of Tl ~then Z is Mn + P;
C ~ is Bi or Te; and wherei~ a is 0.01 to 5 b is 0~1 t~ 20 c is 0.1 to ~0 d is 0.1 to 20 e ls 0.1 to 20; and x ls a value such that the valence requlre-ment of the elements in the catalyst for oxy~en are satisfied.
Tn this catalyst compositlon, the Z comDonent is com?osed of systems o~ two or more speclried elements. In these systems as described above, each element of the system is present ir. an amount of at least l atom percent, pre~er-
. ~atal~sts for the oxidation, ammoxldation and oxvdeh~dro~enatlon Or olefins are well known. See t f~r example, U.S. 3~642,930 and U. S. 3,414,631. Although these catalysts of the art are very desirable, the ca$alysts 10~ of the present invention have significant advantages over these other ~atalysts~
~ .
., SU~IARY AN3 DE~AIL~D DESCRIP~IO~ O~ THE I~ IO~J
The present lnvention is based on the discovery ~hat certain oxldztion catalysts based on iron, bismuth and ~olybde~um and contalnin~ additiona~ speclfied promoter elements exhiblt excellent catalytic activlty for a variety o~ ole~ln oxidatlon, ammoxldatlon, dehydrogenation and oxydehydrogenatlon reactlons. In particular, lt has been round that speci~ic catalytlc compositions as descrlbed `
~ ~ 3 ~ (5-_7~
below are es~e~i211y suited for use in prcducln~ acr~'-o-nitrile and m~thacrylonitrlle by the amms~ld2tion Or propyl-ene and isobutylene, resDectively. In addition to being excellent am~oxidation ca~alysts for the production of acrylonitrile or methacrylonitrile, these catalysts aiso exhibit excellent catalytic activity for the conversion of olerins having four or more contiguous carbon 2toms to the corresponding dioiefins, and in the oxydehydro~enatior. of ole~ins to diolefins.
l~ In accordance with the present invention, novel catalysts having improved catalytic propert~es are repre-sented by the following empirical formula a~b7~cFe~DeMol2ox wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is ~o, Ni, Zn, Cd, Be, r~, Ca, Sr, Ba, ~a or mixtures thereof;
Z is a two-or-more element system selected from the group consisting o~ ~7e T Sb, Cu + W~
Cu + Sn, Ce + W, Pr + ~n, Sn + r'n, ~'r + t~
W + Sb, Cr ~ Sn, W + Sn, Ge + Sn, Sb + Sn, W ~ P, Sb ~ P, Cr + Cu, Mn + Cu, Sb + Cu, ~n + P or mlxtures thereof, with the proviso that said catalyst is free of Tl ~then Z is Mn + P;
C ~ is Bi or Te; and wherei~ a is 0.01 to 5 b is 0~1 t~ 20 c is 0.1 to ~0 d is 0.1 to 20 e ls 0.1 to 20; and x ls a value such that the valence requlre-ment of the elements in the catalyst for oxy~en are satisfied.
Tn this catalyst compositlon, the Z comDonent is com?osed of systems o~ two or more speclried elements. In these systems as described above, each element of the system is present ir. an amount of at least l atom percent, pre~er-
-2-: -- (5~27~
ably at least 5 a'om percent, based on the atoms in the I particular system selected. In this ca~alyst, ~ is prefer-ably Bi.
Preferably, the catalysts of this invention con-tains the above-indicated elements in the following amounts:
a is 0.01 to 0.5, b is 0.1 to 20, :~ c is 0.1 to 9, d is 0.1 to 20, and e is 0.1 to 20.
Optimally the elements are present in the following amourlts:
a is 0.03 to 0.5, b is 4 to 10, c is 0.5 to 7, d is 0.5 to 5, and e is 0.5 to 5.
In a particularly preferred embodiment, the fore-: going preferred and optimal catalysts contain K. Rb and/or ~; Cs and optionally r~i and/or Co.
-.~ 20 Also, lt is desirable if Z is selected so that the C ratio of the amount of ~he first element of each system as described above to the amount of second element in the sy3tem is 1:0.25 to 1:0.75.
Of the foregoing catalysts, catalyst in which the Z component ls selected from the following combinations of elements are of special interest: Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn and Mn + W; while those catalysts in which Z is one of Ge + Sb, Cu + W, Cu + Sn, Ce I W and Pr - f Mn are particularly noteworthy.
ably at least 5 a'om percent, based on the atoms in the I particular system selected. In this ca~alyst, ~ is prefer-ably Bi.
Preferably, the catalysts of this invention con-tains the above-indicated elements in the following amounts:
a is 0.01 to 0.5, b is 0.1 to 20, :~ c is 0.1 to 9, d is 0.1 to 20, and e is 0.1 to 20.
Optimally the elements are present in the following amourlts:
a is 0.03 to 0.5, b is 4 to 10, c is 0.5 to 7, d is 0.5 to 5, and e is 0.5 to 5.
In a particularly preferred embodiment, the fore-: going preferred and optimal catalysts contain K. Rb and/or ~; Cs and optionally r~i and/or Co.
-.~ 20 Also, lt is desirable if Z is selected so that the C ratio of the amount of ~he first element of each system as described above to the amount of second element in the sy3tem is 1:0.25 to 1:0.75.
Of the foregoing catalysts, catalyst in which the Z component ls selected from the following combinations of elements are of special interest: Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn and Mn + W; while those catalysts in which Z is one of Ge + Sb, Cu + W, Cu + Sn, Ce I W and Pr - f Mn are particularly noteworthy.
3 ~he catalysts of this invention can be prepared in any conventional manner known in the art, such as ~or example the various techniques shown in the patents and -3- .
~,~27 applications referred to in the 3ACXGROU~IJ~ OF T:i~ IN~_}TQI5l7~
~or exam?le, the catalysts can be made by ~orming an aqueou-com~osition of decomposable salts and/or oxides of the metals to be incorporated into the catalyst, evapora inO the water from the aqueous composition to form ~ thick pas~e, drying the thick paste and then calcining the thick ~as e at elevated temperature in an oxidizing atmosphere. mechniques for forming catalysts of the type described herein are well Xnown in the art, and those skilled in the art should have no difficulty in making catalysts of the invention.
The catalysts of the present invention may be used unsup~orted or supported on various conventional carriers such as SiO2, A1203, 7r~2~ T~02~ ~ 4 morillonite, or the like. They may be used in fixed-bed or fluid-bed reactors as desired. When using these catalysts, they are simply substituted for the catalysts previously employed, and the reaction is conducted under substantially the same conditions.
For example~ when the inventive catalysts are used in the ammoxidation o~ propylene or isobutylene to form acrylonitrile or methacrylonitrile, respectively, the olefin C to be reacted together with oxygen and ammonia in conven-tlonal proportions are contacted with the catalyst at an elevated temperature, usually about 200-60ac, in a ~ixed or fluid-bed reactor for a time sufficient to e~fect the appro~riate ammoxidation reaction. Similarly, when the inventive catalysts are employed to catalyze other well known reactions, the reaction conditions employed are those which are conventional.
SPECIFIC EMBODIMENTS
Comparat~ve E~amDle A
80~ Ko lNi2 sC4 sFe33iPo.5M0l20x 2 . .
A sol~tion of 127.1 g. ammonium heptamolybd2te ~ 4)6r~io7~24-4.~20 2nd wa er W25 prepa~ed. To tnis solut~on w2s added 6.9 b of a 42.5~ solutlon of H3PO4 and 102.7 g.
of ~lco 40~ silica sol to form a slu~ry. Serarately, an aqueous solu~ion containing 72.7 g. ferric nitra'e, ~e(~!03)~ -9~2i 29.1 g. bismuth nitrate, Bi~N03)3 5.~20: 78-6 g. cobalt nitrate Co(.~03)2 c:~20; 43.6 g. nickel nitrate ~ 03)2-~.2C:
and 6.1 g. of a 10~ potass~um nitrate solution was orep2red.
The solution of metal nitrates was slowly added tc the slurry. The resulting slurry was evaporated to dryness, and the solid obtzined was heat treated at 290C for three hours, at 425C for three hours and at 550C for 16 hou~s.
Examrles 1 to 7 In the same manner as discussed in Compara~ive Example A, catalysts listed in the following ~ABLE I were prepared. Each of these catalysts as well as Comparative Catalyst A W2S tested for its catalytic activity in the ammoxidation of propylene to acrylonitrile. In carrying out this test, each of the catalysts was charged into a 5 cc.
flxed-bed reactor. A reed of propylene/ammonia/oxygen/
nitrogen/steam in amounts of 1.8/2.2/3.6/2.4/6 was fed to the reactor such that the l~WH was 0.1 g. propylene per gram ; catalyst per hour and the contact time was three seconds.
The reaction tem~erature was maintained at 420C. lhe results obtained as well as the results obtained when Comparative Catalyst A was employed was se~ forth in the ; following TABLE I.
. ~
u -~
u~ * ;:
~ C~
c r~
~O
h ~ e ~ o o _1 tO ~ 0~) C~ ~ ~ ~ r~
r~ ~ I` X O` I` I~ r~
u C cO~
Y
.~ .
^l O~ J
,/ X ^ ^ ^ ^ ,_ ~ ~
O X ~
C
e o 9 1:~
G ,., u C~ .
LJ O U~
~ ~ ~ O O
Ei C~
O _, o u~
C; ~r, ~; ~ 0 . ~ _I
U~ 0 ~ Z _ C ~
t~ C
v u . ~ ~ ~' ~
e Z . . . ~ C ~
~ --I ~O O O ~ C . U
O 3 c~ 3 3 ~ E: o "~
~, Y ~ C~ c4 ~ E
w ~1 C~ ¢
= ~.
s~ _ ~
X ~
0~73 The parentheses used in -TABLE I as well as tAe follo~,Ji~g TABLr TI have no signific2nce other than to clarlry the difference betwe-n the various catalysts.
_xam~les 8 to lQ
.
Using the various catalysts prepared in the m_nner described above, additional examples in which propylene was ammoxidized to acrylonitrile were conducted. These addi-tional experi~ents were conducted in accordance with the same procedure used in F.xamples 1 to 7, except that the reaction temDerature was 430~ the contact time was 6 seconds and the catal,yst support was 50~ Si~2. The results obtained are set forth in the following TABLE II.
c ~ t3,~
.j_, U~ *
. ~ ~ o r~ 0 .~.j cl P~
C;
~ ~o ~J o o o 5~
0 ~ 0 0 4 ~rl L r~ I~I~ C~ Cl? --U
'~ C
: o G
: .
e , X ^ ~ 'I
: ~ OX cX C~l ~
O C X ~
V ~ ~ . ~
.,, V o o . -O o .~ ~' 0 C C~
ci _i CJ
U V:
' V V U~ U~ .z U~ ~ ~-;` C C
~, ~, U~ ~ . o ' ~ ~ . K", , 31 c c o X 0~ 0-- C~
W ~ *
~,~27 applications referred to in the 3ACXGROU~IJ~ OF T:i~ IN~_}TQI5l7~
~or exam?le, the catalysts can be made by ~orming an aqueou-com~osition of decomposable salts and/or oxides of the metals to be incorporated into the catalyst, evapora inO the water from the aqueous composition to form ~ thick pas~e, drying the thick paste and then calcining the thick ~as e at elevated temperature in an oxidizing atmosphere. mechniques for forming catalysts of the type described herein are well Xnown in the art, and those skilled in the art should have no difficulty in making catalysts of the invention.
The catalysts of the present invention may be used unsup~orted or supported on various conventional carriers such as SiO2, A1203, 7r~2~ T~02~ ~ 4 morillonite, or the like. They may be used in fixed-bed or fluid-bed reactors as desired. When using these catalysts, they are simply substituted for the catalysts previously employed, and the reaction is conducted under substantially the same conditions.
For example~ when the inventive catalysts are used in the ammoxidation o~ propylene or isobutylene to form acrylonitrile or methacrylonitrile, respectively, the olefin C to be reacted together with oxygen and ammonia in conven-tlonal proportions are contacted with the catalyst at an elevated temperature, usually about 200-60ac, in a ~ixed or fluid-bed reactor for a time sufficient to e~fect the appro~riate ammoxidation reaction. Similarly, when the inventive catalysts are employed to catalyze other well known reactions, the reaction conditions employed are those which are conventional.
SPECIFIC EMBODIMENTS
Comparat~ve E~amDle A
80~ Ko lNi2 sC4 sFe33iPo.5M0l20x 2 . .
A sol~tion of 127.1 g. ammonium heptamolybd2te ~ 4)6r~io7~24-4.~20 2nd wa er W25 prepa~ed. To tnis solut~on w2s added 6.9 b of a 42.5~ solutlon of H3PO4 and 102.7 g.
of ~lco 40~ silica sol to form a slu~ry. Serarately, an aqueous solu~ion containing 72.7 g. ferric nitra'e, ~e(~!03)~ -9~2i 29.1 g. bismuth nitrate, Bi~N03)3 5.~20: 78-6 g. cobalt nitrate Co(.~03)2 c:~20; 43.6 g. nickel nitrate ~ 03)2-~.2C:
and 6.1 g. of a 10~ potass~um nitrate solution was orep2red.
The solution of metal nitrates was slowly added tc the slurry. The resulting slurry was evaporated to dryness, and the solid obtzined was heat treated at 290C for three hours, at 425C for three hours and at 550C for 16 hou~s.
Examrles 1 to 7 In the same manner as discussed in Compara~ive Example A, catalysts listed in the following ~ABLE I were prepared. Each of these catalysts as well as Comparative Catalyst A W2S tested for its catalytic activity in the ammoxidation of propylene to acrylonitrile. In carrying out this test, each of the catalysts was charged into a 5 cc.
flxed-bed reactor. A reed of propylene/ammonia/oxygen/
nitrogen/steam in amounts of 1.8/2.2/3.6/2.4/6 was fed to the reactor such that the l~WH was 0.1 g. propylene per gram ; catalyst per hour and the contact time was three seconds.
The reaction tem~erature was maintained at 420C. lhe results obtained as well as the results obtained when Comparative Catalyst A was employed was se~ forth in the ; following TABLE I.
. ~
u -~
u~ * ;:
~ C~
c r~
~O
h ~ e ~ o o _1 tO ~ 0~) C~ ~ ~ ~ r~
r~ ~ I` X O` I` I~ r~
u C cO~
Y
.~ .
^l O~ J
,/ X ^ ^ ^ ^ ,_ ~ ~
O X ~
C
e o 9 1:~
G ,., u C~ .
LJ O U~
~ ~ ~ O O
Ei C~
O _, o u~
C; ~r, ~; ~ 0 . ~ _I
U~ 0 ~ Z _ C ~
t~ C
v u . ~ ~ ~' ~
e Z . . . ~ C ~
~ --I ~O O O ~ C . U
O 3 c~ 3 3 ~ E: o "~
~, Y ~ C~ c4 ~ E
w ~1 C~ ¢
= ~.
s~ _ ~
X ~
0~73 The parentheses used in -TABLE I as well as tAe follo~,Ji~g TABLr TI have no signific2nce other than to clarlry the difference betwe-n the various catalysts.
_xam~les 8 to lQ
.
Using the various catalysts prepared in the m_nner described above, additional examples in which propylene was ammoxidized to acrylonitrile were conducted. These addi-tional experi~ents were conducted in accordance with the same procedure used in F.xamples 1 to 7, except that the reaction temDerature was 430~ the contact time was 6 seconds and the catal,yst support was 50~ Si~2. The results obtained are set forth in the following TABLE II.
c ~ t3,~
.j_, U~ *
. ~ ~ o r~ 0 .~.j cl P~
C;
~ ~o ~J o o o 5~
0 ~ 0 0 4 ~rl L r~ I~I~ C~ Cl? --U
'~ C
: o G
: .
e , X ^ ~ 'I
: ~ OX cX C~l ~
O C X ~
V ~ ~ . ~
.,, V o o . -O o .~ ~' 0 C C~
ci _i CJ
U V:
' V V U~ U~ .z U~ ~ ~-;` C C
~, ~, U~ ~ . o ' ~ ~ . K", , 31 c c o X 0~ 0-- C~
W ~ *
Claims (23)
1. A catalyst of the formula:
JaQbZcFedDeMo12MoX
wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is Co, Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof;
Z is a two-or-more element system comprising Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn, Mn + W, W + Sb, Cr + Sn, 11 + Sn, Ge +
Sn, Sb + Sn, W + P, Sb + P, Cr + Cu, Mn + Cu, Sb + Cu, Mn + P or mixtures thereof with the proviso that said catalyst is free of T1 when Z is Mn + P;
D is Bi or Te; and wherein 0.01 ? a ? 5 0.1 ? b ? 20 0.1 ? c ? 20 0.1 ? d ? 20 0.1 ? e ? 20; and x is a value such that the valence require-ment of the elements in the catalyst for oxygen are satisfied;
each element in said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
JaQbZcFedDeMo12MoX
wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is Co, Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof;
Z is a two-or-more element system comprising Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn, Mn + W, W + Sb, Cr + Sn, 11 + Sn, Ge +
Sn, Sb + Sn, W + P, Sb + P, Cr + Cu, Mn + Cu, Sb + Cu, Mn + P or mixtures thereof with the proviso that said catalyst is free of T1 when Z is Mn + P;
D is Bi or Te; and wherein 0.01 ? a ? 5 0.1 ? b ? 20 0.1 ? c ? 20 0.1 ? d ? 20 0.1 ? e ? 20; and x is a value such that the valence require-ment of the elements in the catalyst for oxygen are satisfied;
each element in said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
2. The catalyst of claim 1 wherein 0.01 ? a ? 0.5 and 0.1 ? c ? 9.
3. The catalyst of claim 2 wherein D is Bi.
4. The catalyst of claim 3 wherein Z is Ge + Sb.
5. The catalyst of claim 3 wherein Z is Cu + W.
6. The catalyst of claim 3 wherein Z is Cu + Sn.
7. The catalyst of claim 3 wherein Z is Ce + W.
8. The catalyst of claim 3 wherein Z is Pr + Mn.
(502
(502
9 . The catalyst of claim 3 wherein Z is Sn + Mn.
10 . The catalyst of claim 3 wherein Z is Mn + W.
11 . The catalyst of claim 3 wherein said catalyst contains at least one of K, Pb, and Cs and at least one of Co and Ni.
12 . The catalyst of claim 3 wherein Z is W + Sb.
13 . The catalyst of claim 3 wherein Z is Cr + Sn.
14 . The catalyst of claim 3 wherein 7. is W + Sn.
15 . The catalyst of claim 3 wherein Z is Ge + Sn.
16 . The catalyst of claim 3 wherein Z is Sb + Sn.
17 . The catalyst of claim 3 wherein Z is W + P.
18 . The catalyst of claim 3 wherein Z is Sb + P.
19 . The catalyst of claim 3 wherein Z is Cr + Cu.
20 . The catalyst of claim 3 wherein Z is Mn. + Cu.
21. The catalyst of claim 3 wherein Z is Sb + Cu.
22 . The catalyst of claim wherein Z is Mn + P.
23 . In a process for the preparation of acrylo-nitrile or methacrylonitrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200°C to 600°C in the presence of a catalyst, the improvement comprising using as the catalyst a catalyst of the formula:
JaQbZcFedDeMo12OX
wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is Co, Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof;
Z is a two-or-more element system comprising Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mr, Sn + Mn, Mn + W, W + Sb, Cr + Sn, W + Sn, Ge +
Sn, Sb + Sn, W + P, Sb + P, Cr + Cu, Mn + Cu, Sb + Cu, Mn + P or mixtures thereof with the proviso that said catalyst is free of Tl when Z is Mn + P
D is Bi or Te; and (5027) wherein0.1 ? a ? 5;
0.1 ? b ? 20, 0.1 ? c ? 20;
0.1 ? d ? 20;
0.1 ? e ? 20; and x is a value such that the valence require-ment of the elements in the catalyst for oxygen are satisfied;
each element is said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
JaQbZcFedDeMo12OX
wherein J is an alkali metal, thallium, silver or mixtures thereof;
Q is Co, Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof;
Z is a two-or-more element system comprising Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mr, Sn + Mn, Mn + W, W + Sb, Cr + Sn, W + Sn, Ge +
Sn, Sb + Sn, W + P, Sb + P, Cr + Cu, Mn + Cu, Sb + Cu, Mn + P or mixtures thereof with the proviso that said catalyst is free of Tl when Z is Mn + P
D is Bi or Te; and (5027) wherein0.1 ? a ? 5;
0.1 ? b ? 20, 0.1 ? c ? 20;
0.1 ? d ? 20;
0.1 ? e ? 20; and x is a value such that the valence require-ment of the elements in the catalyst for oxygen are satisfied;
each element is said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81973277A | 1977-07-28 | 1977-07-28 | |
| US819,732 | 1977-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132124A true CA1132124A (en) | 1982-09-21 |
Family
ID=25228901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA306,799A Expired CA1132124A (en) | 1977-07-28 | 1978-07-05 | Oxidation catalysts |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0000564B1 (en) |
| AT (1) | AT363911B (en) |
| AU (1) | AU525163B2 (en) |
| BR (1) | BR7804847A (en) |
| CA (1) | CA1132124A (en) |
| DD (1) | DD137532A5 (en) |
| DE (1) | DE2861849D1 (en) |
| DK (1) | DK333778A (en) |
| EG (1) | EG13970A (en) |
| ES (1) | ES471682A1 (en) |
| FI (1) | FI66129C (en) |
| GR (1) | GR66444B (en) |
| IE (1) | IE47301B1 (en) |
| IL (1) | IL55073A (en) |
| IN (1) | IN148019B (en) |
| IT (1) | IT1196394B (en) |
| NO (1) | NO150345C (en) |
| PT (1) | PT68312A (en) |
| RO (1) | RO77761A (en) |
| ZA (1) | ZA783914B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1127137A (en) * | 1977-12-20 | 1982-07-06 | Dev D. Suresh | Ammoxidation of olefins with novel antimonate catalysts |
| US4316855A (en) * | 1979-12-28 | 1982-02-23 | The Standard Oil Co. | Multiply promoted Sn-Sb oxide catalysts |
| EP0044875B1 (en) * | 1980-07-18 | 1984-06-13 | Mitsubishi Kasei Corporation | Catalytic composition, method for its preparation and its use |
| DE3376529D1 (en) * | 1982-09-30 | 1988-06-16 | Monsanto Co | Catalysts for the oxidation and ammoxidation of alcohols |
| US4469810A (en) * | 1983-01-11 | 1984-09-04 | Mitsubishi Rayon Company Limited | Process for the calcination of phosphorus-molybdenum catalyst |
| GB2221852A (en) * | 1988-08-18 | 1990-02-21 | Ti Corporate Services | Vehicle exhaust gas catalysts |
| US5093299A (en) * | 1990-01-09 | 1992-03-03 | The Standard Oil Company | Catalyst for process for the manufacture of acrylonitrile and methacrylonitrile |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5112603B1 (en) * | 1971-05-26 | 1976-04-21 | ||
| CA1004232A (en) * | 1971-12-30 | 1977-01-25 | The Standard Oil Company | Coproduction of methacrylonitrile and butadiene |
| CA1049553A (en) * | 1973-04-30 | 1979-02-27 | The Standard Oil Company | Preparation of acrylic acid and methacrylic acid from propylene or isobutylene in a one-reactor, fluid-bed system |
| NL171440C (en) * | 1973-05-10 | 1983-04-05 | Japan Synthetic Rubber Co Ltd | PROCESS FOR PREPARING METHACROLES BY CATALYTIC OXYDATION OF ISOBUTENE. |
| DE2424934A1 (en) * | 1973-06-04 | 1975-01-02 | Standard Oil Co Ohio | METHOD OF CATALYTIC PRODUCTION OF UNSATATULATED NITRILES |
| US3972920A (en) * | 1973-06-11 | 1976-08-03 | Mitsubishi Rayon Co., Ltd. | Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes |
| US3883573A (en) * | 1973-06-15 | 1975-05-13 | Standard Oil Co | Commercial fixed-bed acrylonitrile or methacrylonitrile |
| CH569926A5 (en) * | 1973-06-15 | 1975-11-28 | Bartolomeis Spa Forni Ed Impia | |
| US3932551A (en) * | 1973-10-12 | 1976-01-13 | The Standard Oil Company | Process for the preparation of diolefins from olefins |
| US4001317A (en) * | 1974-07-22 | 1977-01-04 | Standard Oil Company | Process for the oxidation of olefins using catalysts containing various promoter elements |
| GB1523772A (en) * | 1974-07-22 | 1978-09-06 | Standard Oil Co | Oxidation catalysts |
| GB1489559A (en) * | 1975-03-03 | 1977-10-19 | Mitsubishi Rayon Co | Catalytic process for the preparation of acrylic acid or methacrylic acid |
| GB1490683A (en) * | 1975-03-12 | 1977-11-02 | Mitsubishi Rayon Co | Process and a catalyst for producing unsaturated aldehydes unsaturated carboxylic acids or conjugated diene |
| IN142430B (en) * | 1975-04-21 | 1977-07-09 | Standard Oil Co | |
| US4118419A (en) * | 1975-12-03 | 1978-10-03 | Mitsubishi Rayon Company, Ltd. | Catalytic process for the preparation of an unsaturated carboxylic acid |
| DE2626887B2 (en) * | 1976-06-16 | 1978-06-29 | Basf Ag, 6700 Ludwigshafen | Catalyst for the oxadation of (methacrolein to (meth) acrylic acid |
| US4335264A (en) * | 1976-07-07 | 1982-06-15 | E. I. Du Pont De Nemours And Company | High yield, low byproduct α, β-unsaturated aldehydes from olefins |
| US4065507A (en) * | 1976-08-02 | 1977-12-27 | Standard Oil Company | Preparation of methacrylic derivatives from tertiary butyl-containing compounds |
-
1978
- 1978-07-04 IL IL55073A patent/IL55073A/en unknown
- 1978-07-05 GR GR56696A patent/GR66444B/el unknown
- 1978-07-05 CA CA306,799A patent/CA1132124A/en not_active Expired
- 1978-07-07 ZA ZA00783914A patent/ZA783914B/en unknown
- 1978-07-07 IN IN507/DEL/78A patent/IN148019B/en unknown
- 1978-07-11 AU AU37930/78A patent/AU525163B2/en not_active Expired
- 1978-07-13 ES ES471682A patent/ES471682A1/en not_active Expired
- 1978-07-18 PT PT68312A patent/PT68312A/en unknown
- 1978-07-19 FI FI782285A patent/FI66129C/en not_active IP Right Cessation
- 1978-07-21 DE DE7878100469T patent/DE2861849D1/en not_active Expired
- 1978-07-21 EP EP78100469A patent/EP0000564B1/en not_active Expired
- 1978-07-25 DD DD78206917A patent/DD137532A5/en unknown
- 1978-07-26 EG EG459/78A patent/EG13970A/en active
- 1978-07-26 DK DK333778A patent/DK333778A/en not_active Application Discontinuation
- 1978-07-26 IT IT26142/78A patent/IT1196394B/en active
- 1978-07-27 NO NO782582A patent/NO150345C/en unknown
- 1978-07-27 IE IE1523/78A patent/IE47301B1/en unknown
- 1978-07-27 RO RO7894814A patent/RO77761A/en unknown
- 1978-07-27 AT AT0547778A patent/AT363911B/en not_active IP Right Cessation
- 1978-07-27 BR BR7804847A patent/BR7804847A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO150345B (en) | 1984-06-25 |
| ZA783914B (en) | 1979-08-29 |
| PT68312A (en) | 1978-08-01 |
| EP0000564A1 (en) | 1979-02-07 |
| AU525163B2 (en) | 1982-10-21 |
| GR66444B (en) | 1981-03-23 |
| EP0000564B1 (en) | 1982-05-19 |
| FI782285A (en) | 1979-01-29 |
| FI66129C (en) | 1984-09-10 |
| RO77761A (en) | 1981-11-24 |
| IE781523L (en) | 1979-01-28 |
| AU3793078A (en) | 1980-01-17 |
| BR7804847A (en) | 1979-04-10 |
| EG13970A (en) | 1983-03-31 |
| FI66129B (en) | 1984-05-31 |
| IT7826142A0 (en) | 1978-07-26 |
| DE2861849D1 (en) | 1982-07-08 |
| ES471682A1 (en) | 1979-10-01 |
| AT363911B (en) | 1981-09-10 |
| DK333778A (en) | 1979-01-29 |
| DD137532A5 (en) | 1979-09-12 |
| ATA547778A (en) | 1981-02-15 |
| NO782582L (en) | 1979-01-30 |
| IE47301B1 (en) | 1984-02-22 |
| IL55073A (en) | 1982-01-31 |
| NO150345C (en) | 1984-10-03 |
| IN148019B (en) | 1980-09-27 |
| IT1196394B (en) | 1988-11-16 |
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