CA1055468A - Catalyst compositions especially useful for preparation of unsaturated acids - Google Patents
Catalyst compositions especially useful for preparation of unsaturated acidsInfo
- Publication number
- CA1055468A CA1055468A CA215,156A CA215156A CA1055468A CA 1055468 A CA1055468 A CA 1055468A CA 215156 A CA215156 A CA 215156A CA 1055468 A CA1055468 A CA 1055468A
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- Canada
- Prior art keywords
- catalyst
- catalysts
- mixture
- catalyst composition
- acrolein
- 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.)
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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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J23/30—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
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
CATALYST COMPOSITIONS ESPECIALLY
USEFUL FOR PREPARATION OF UNSATURATED ACIDS
ABSTRACT OF THE DI DISCLOSURE
The present invention is a catalyst composition consisting of oxides or oxide complexes that contains catalytically significant amounts of uranium or thorium plus, tungsten, vanadium and molybdenum plus optionally one or more of Co, Fe, Ni, ZN, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P
an alkali metal, an alkaline earth metal, lanthanum or an element of the lantbanoid series. These catalysts are especially useful for producing acrylic acid from acrolein and for producing methacrylic acid from methacrolein.
USEFUL FOR PREPARATION OF UNSATURATED ACIDS
ABSTRACT OF THE DI DISCLOSURE
The present invention is a catalyst composition consisting of oxides or oxide complexes that contains catalytically significant amounts of uranium or thorium plus, tungsten, vanadium and molybdenum plus optionally one or more of Co, Fe, Ni, ZN, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P
an alkali metal, an alkaline earth metal, lanthanum or an element of the lantbanoid series. These catalysts are especially useful for producing acrylic acid from acrolein and for producing methacrylic acid from methacrolein.
Description
BACKGROUND_OF THE INVENTION
Catalyst compositions similar to those of the invention are known, see U. S. 3,567,773 which shows catalysts containing WVMo. The present invention adds uranium or thorium to these catalysts and obtains unexpectedly dasirable catalysts for producing acrylic acid and methacrylic acidO
The production of acrylic acid by the oxidation of acrolein and the production of methacrylic acid by the oxidation of methacrolein are known in the art. With respect to these processes, the present invention employs the known art process but substitutes the catalysts of the invention for the catalysts of the artO
.
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' i54~ -SUMMARY OF rHE INVENTION
The present in~ention is a catalyst composition consisting of oxides or oxide complexes that contains catalytica}ly-s significant amounts of uranium~ thorium or mixture thereof, tungsten, vanadium and molybdenum plus optionally one or more of Co, Fe, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or an element of the lanthanoid series. These catalysts are especially effective for preparing acrylic acid from acrolein and the preparation of methacrylic acid from methacrolein. The catalysts are also highly effective for oxidation reactions such as the oxida~ion of butadiene to maleic anhydride and the oxidative esterification of unsaturated aldehydes to the corresponding unsaturated ester. The catalysts of the invention are highly reactive I
and are capable of very selectively oxidizing acrolein to ~1 acrylic acid at low temperatures~lth little or no acetic acid production.
The invention is the catalyst compositionO
The basic invention is a catalyst containing uranium, thorium or mixture thereof, tungsten, vanadium and molybdenum.
The other possible elements of the catalyst are optionally included.
As noted above~ ~atalysts very slmilar to the ~li catalysts of the invention are known~ see for example U~ S. 3~567~773. Moreo~er~ catalysts of the general type of the catalysts are known and a person of ordinary skill in the art needs no more than the description of the elements in the catalyst to prepare catalysts claimed by ,, .
,, .
~ : . , , ,.,.,.: ,,- , '~ " ''' ' ' .
~ 55~68 the present invention. Thus, the broad description of the invention makes the catalysts of the invention available.
Normallyg the catalysts of the invention are prepared by mixing the catalyst ingredients in the proper proportions in an aqueous mixture, drying the resulting aqueous slurry and calcining the product. The ingredients going into the preparation of the catalysts can be the oxides, halides, nitrates or other salts of the particular compound added. If a support is used, the material comprising the support is usually incorporated into the catalyst along with the other ingredients. After the catalyst ingredients have been combined to form an aqueous slurry, the slurry is evaporated to dryness, and the dried solid obtained is heated in the presence of air at temperatures between about 200 and 600C. This calcination can take place outside ..
of the catalytic reactor or an in situ activation could be~tilized.
Although there are a number of preparations that could be used to make desirable catalysts of the invention, catalysts that contain molybdenum in a partially reduced state below hexavalent molybdenum are preferred.
The preparation of catalysts of the invention containing reduced molybdenum is shown in the Specific Embodiments.
The broad composition of the catalyst i5 described above. With respect to the composition, there are certain preferred embodiments~ Preferred are those catalysts wherein more than about 50V/o of the atoms~ exclusive of oxygen and any support material~ are molybdenum. Also~ wlth respect :' ''''' .
: ..
' ' ' ,: ' " ' ' . . , ' , , '. ', ''' ' ' ' ' ,' :, ~0554~B
to the broad description, those catalysts having no optional components or optional components of Fe7 Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof are preferred.
In terms of a specific empirical formula, the catalysts of the invention are described by the following formula:
Aa~ 'b WC Vd Me x wherein A is Co, Fe, Ni, Zn, Cu, Mg, Mn, si, Ti, Zr, Sn, P, an alkali metal an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is urani~n, thorium or mixture thereof;
and wherein a is 0 to about 5;
b~ c and d are about 0.1 to about 10;
~! e is a number of about 6 to about 16; and x is the number of oxy~gens required to satisfy the valence requirements of the other elements present~
Referring to the formula, preferred catalysts are designated when A is Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof and when a is greater than zero. Indlvidual optional elements represented by A which are preferred are copper and cobalt.
In addition to the active catalytic ingredlents~
the catalysts of the invention may contaln a support material~
- Suitable support materials include silica, alumina, zirconia~
titania~ silicon carbide~ boron phosphate and the like.
A preferred support material is silica.
As noted above~ the catalysts of the invention ~-are useful in a number of different oxidation reactions.
Preeerred emoDe the~e reactions Ls the produceion Oe , :
,, .
:IqD5S~
unsaturated acids from the corresponding unsaturated aldehyde.
In such a process, acrylic acid or methacrylic acid is produced by reacting acrolein or methacrolein with molecular oxygen tn the presence of steam at a temperature of about 200 to about 500C. Of special interest is the preparation of acrylic acid from acrolein because of the extremely desirable results obtained.
The oxidation of unsaturated aldehydes to obtain the corresponding acid is well known in the art. Basically, the invention, with respect to the process~ is the use of the new cataly~t within the parameters of the known art process.
The known process in~olves the contacting of the unsaturated aldehyde with molecular oxygen in the presence -~
of steam at a temperature of about 200 to about 500C.
The ratio of the reactants may vary widely with molar i ratios of molecular oxygen to aldehyde of about 0.5 to f about 5 moles normally being employed. Molecular oxygen is most conveniently added as air. The amount of steam may vary widely from the small amount generated in the reaction to 20 or more moles of steam per mole of aldehyde.
In the preerred practice of the invention3 about 1 to about 10 moles of steam are added to the reactant feed.
f The reaction may be conducted in a fixed- or I fluid-bed re3ctor using atmospheric, superatmospheric or :f subatmospheric pressure. The apparent contact time may i~ vary considerably with contact times of a fraction of a second to 20 ~ecDnds of =ore nDrmally being mployed.
~5-:
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...... .. .. . ........ .... . ... ... ... ... ..... ... .. .
,''','" ' ''''"" ' '"""'.' "'' "" ' ", ' ' " "' ' ':'' ;''"'" ~'' ', ' ~. ',;' .': '''": ', 5~68 Using the catalyst of the invention, very desir~ble yields of unsaturated acid are obtained at low temperatures with the production of little or no acetic acid.
SPECIFIC EMBODIMENTS
Comparative Example A and Examples 1-3 ~ Catalyst of invention compared to the art.
A base catalyst of the invention was prepared and compared to a catalyst of U. S. 3~567~773~ The catalysts were prepared as follows: -Comparative Example A
62% Wl 2V3Mol20 and 38~/o SiO2 This catalyst was prepared according to Example 6 of U. S. 3~567~773 Examples 1-3 U2~1 2V3Mol20x An aqueous slurry was prepared in 500 cc~ of distilled waterO The slurry contained 72~0 go of MoO3~ 36 g. of V205 and 9~19 g. of tungsten metal powder. The slurry was refluxed for two hours during which the color of the~slurry changed to blue-black.
Separately~ 35 ~ 3 g ~ of U02(C2H302) 2 .2H20 was dissolved in water and added to the slurry. The resulting mixture was refluxed for one hour~ and then evaporated to a paste material. The paste was dried in an o~ern over night at 110C. The catalyst was ground and screened to obtain a 10 to 30 mesh fraction.
The catalysts prepared above were placed in a reactor conatructed of a 1.0 cm. inslde dlameter stainless steel tube-having a reaction ~one of 20 cc. The catalyst -6- ~ ~
:. '' . "
~ : , :,, ,,. , , , . : . .
,~, ,. , ,, , ' ',' ,, ' .' , , ~s5~a68 of the invention was activated for two hours~under an air flow at 400C. The reactor was fed with a mixture of acrolein/airtsteam in the molar ratio of 1/10/6. The temperature of the surrounding heating block and the apparent contact time are given in Table I. The results are also given in Table I using the following definitions:
Single pass yield = _oles of product recovered x 100 moles of acrolein fed Conversion = moles of acrolein reacted x 130 moles of acrolein fed Selectivit m_les of acrylic acid recovered x 100 moles of acrolein reacted :~
~,,' ,.
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' i 7 ; ~ ' '', :, ' - ,' "', ,,, ;, . ' ' '' '. . . ' , ' ' : ' ,, , , . : . . . , . . , ,, ~ , ~; .. .. . , ,,. .,, . . ' ' .' ' : .
,.. . . . . . . ........... . . . .
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~ rl ,, g ~ ~ ~,1 o~ s, ~ C J C~
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,. ~,`, C~~. .
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lOSS468 In the same manner as shown by the examples above, other catalysts of the invention containing thorium instead of uranium or containing different amounts of uranium or thorium and different optional elements, such as Fe, Mn, Ni, Mg and the like, are used to produce acrylic acid.
Moreover, promoted catalysts containing various amounts of tungsten, vanadium and molybdenum are used.
: Also using the catalysts of the invention, maleic anhydride, methacrylic acid or acrylates are made by known oxldation reactlons.
' ..,.
~1 ,.~, ., _ 9_ - :
, .1j 1 ~, .
., ~
.~ .
i ......... . . ~, ~. . .. ... ... . .
Catalyst compositions similar to those of the invention are known, see U. S. 3,567,773 which shows catalysts containing WVMo. The present invention adds uranium or thorium to these catalysts and obtains unexpectedly dasirable catalysts for producing acrylic acid and methacrylic acidO
The production of acrylic acid by the oxidation of acrolein and the production of methacrylic acid by the oxidation of methacrolein are known in the art. With respect to these processes, the present invention employs the known art process but substitutes the catalysts of the invention for the catalysts of the artO
.
'.. , ! ' ' , , ~ ' .' . , , . , . , ,, , ~ , . . . . , . I .
' ', ' .~ . .;, , ' ~ . ' ,.
,: , . .
' i54~ -SUMMARY OF rHE INVENTION
The present in~ention is a catalyst composition consisting of oxides or oxide complexes that contains catalytica}ly-s significant amounts of uranium~ thorium or mixture thereof, tungsten, vanadium and molybdenum plus optionally one or more of Co, Fe, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or an element of the lanthanoid series. These catalysts are especially effective for preparing acrylic acid from acrolein and the preparation of methacrylic acid from methacrolein. The catalysts are also highly effective for oxidation reactions such as the oxida~ion of butadiene to maleic anhydride and the oxidative esterification of unsaturated aldehydes to the corresponding unsaturated ester. The catalysts of the invention are highly reactive I
and are capable of very selectively oxidizing acrolein to ~1 acrylic acid at low temperatures~lth little or no acetic acid production.
The invention is the catalyst compositionO
The basic invention is a catalyst containing uranium, thorium or mixture thereof, tungsten, vanadium and molybdenum.
The other possible elements of the catalyst are optionally included.
As noted above~ ~atalysts very slmilar to the ~li catalysts of the invention are known~ see for example U~ S. 3~567~773. Moreo~er~ catalysts of the general type of the catalysts are known and a person of ordinary skill in the art needs no more than the description of the elements in the catalyst to prepare catalysts claimed by ,, .
,, .
~ : . , , ,.,.,.: ,,- , '~ " ''' ' ' .
~ 55~68 the present invention. Thus, the broad description of the invention makes the catalysts of the invention available.
Normallyg the catalysts of the invention are prepared by mixing the catalyst ingredients in the proper proportions in an aqueous mixture, drying the resulting aqueous slurry and calcining the product. The ingredients going into the preparation of the catalysts can be the oxides, halides, nitrates or other salts of the particular compound added. If a support is used, the material comprising the support is usually incorporated into the catalyst along with the other ingredients. After the catalyst ingredients have been combined to form an aqueous slurry, the slurry is evaporated to dryness, and the dried solid obtained is heated in the presence of air at temperatures between about 200 and 600C. This calcination can take place outside ..
of the catalytic reactor or an in situ activation could be~tilized.
Although there are a number of preparations that could be used to make desirable catalysts of the invention, catalysts that contain molybdenum in a partially reduced state below hexavalent molybdenum are preferred.
The preparation of catalysts of the invention containing reduced molybdenum is shown in the Specific Embodiments.
The broad composition of the catalyst i5 described above. With respect to the composition, there are certain preferred embodiments~ Preferred are those catalysts wherein more than about 50V/o of the atoms~ exclusive of oxygen and any support material~ are molybdenum. Also~ wlth respect :' ''''' .
: ..
' ' ' ,: ' " ' ' . . , ' , , '. ', ''' ' ' ' ' ,' :, ~0554~B
to the broad description, those catalysts having no optional components or optional components of Fe7 Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof are preferred.
In terms of a specific empirical formula, the catalysts of the invention are described by the following formula:
Aa~ 'b WC Vd Me x wherein A is Co, Fe, Ni, Zn, Cu, Mg, Mn, si, Ti, Zr, Sn, P, an alkali metal an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is urani~n, thorium or mixture thereof;
and wherein a is 0 to about 5;
b~ c and d are about 0.1 to about 10;
~! e is a number of about 6 to about 16; and x is the number of oxy~gens required to satisfy the valence requirements of the other elements present~
Referring to the formula, preferred catalysts are designated when A is Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof and when a is greater than zero. Indlvidual optional elements represented by A which are preferred are copper and cobalt.
In addition to the active catalytic ingredlents~
the catalysts of the invention may contaln a support material~
- Suitable support materials include silica, alumina, zirconia~
titania~ silicon carbide~ boron phosphate and the like.
A preferred support material is silica.
As noted above~ the catalysts of the invention ~-are useful in a number of different oxidation reactions.
Preeerred emoDe the~e reactions Ls the produceion Oe , :
,, .
:IqD5S~
unsaturated acids from the corresponding unsaturated aldehyde.
In such a process, acrylic acid or methacrylic acid is produced by reacting acrolein or methacrolein with molecular oxygen tn the presence of steam at a temperature of about 200 to about 500C. Of special interest is the preparation of acrylic acid from acrolein because of the extremely desirable results obtained.
The oxidation of unsaturated aldehydes to obtain the corresponding acid is well known in the art. Basically, the invention, with respect to the process~ is the use of the new cataly~t within the parameters of the known art process.
The known process in~olves the contacting of the unsaturated aldehyde with molecular oxygen in the presence -~
of steam at a temperature of about 200 to about 500C.
The ratio of the reactants may vary widely with molar i ratios of molecular oxygen to aldehyde of about 0.5 to f about 5 moles normally being employed. Molecular oxygen is most conveniently added as air. The amount of steam may vary widely from the small amount generated in the reaction to 20 or more moles of steam per mole of aldehyde.
In the preerred practice of the invention3 about 1 to about 10 moles of steam are added to the reactant feed.
f The reaction may be conducted in a fixed- or I fluid-bed re3ctor using atmospheric, superatmospheric or :f subatmospheric pressure. The apparent contact time may i~ vary considerably with contact times of a fraction of a second to 20 ~ecDnds of =ore nDrmally being mployed.
~5-:
.. . .
...... .. .. . ........ .... . ... ... ... ... ..... ... .. .
,''','" ' ''''"" ' '"""'.' "'' "" ' ", ' ' " "' ' ':'' ;''"'" ~'' ', ' ~. ',;' .': '''": ', 5~68 Using the catalyst of the invention, very desir~ble yields of unsaturated acid are obtained at low temperatures with the production of little or no acetic acid.
SPECIFIC EMBODIMENTS
Comparative Example A and Examples 1-3 ~ Catalyst of invention compared to the art.
A base catalyst of the invention was prepared and compared to a catalyst of U. S. 3~567~773~ The catalysts were prepared as follows: -Comparative Example A
62% Wl 2V3Mol20 and 38~/o SiO2 This catalyst was prepared according to Example 6 of U. S. 3~567~773 Examples 1-3 U2~1 2V3Mol20x An aqueous slurry was prepared in 500 cc~ of distilled waterO The slurry contained 72~0 go of MoO3~ 36 g. of V205 and 9~19 g. of tungsten metal powder. The slurry was refluxed for two hours during which the color of the~slurry changed to blue-black.
Separately~ 35 ~ 3 g ~ of U02(C2H302) 2 .2H20 was dissolved in water and added to the slurry. The resulting mixture was refluxed for one hour~ and then evaporated to a paste material. The paste was dried in an o~ern over night at 110C. The catalyst was ground and screened to obtain a 10 to 30 mesh fraction.
The catalysts prepared above were placed in a reactor conatructed of a 1.0 cm. inslde dlameter stainless steel tube-having a reaction ~one of 20 cc. The catalyst -6- ~ ~
:. '' . "
~ : , :,, ,,. , , , . : . .
,~, ,. , ,, , ' ',' ,, ' .' , , ~s5~a68 of the invention was activated for two hours~under an air flow at 400C. The reactor was fed with a mixture of acrolein/airtsteam in the molar ratio of 1/10/6. The temperature of the surrounding heating block and the apparent contact time are given in Table I. The results are also given in Table I using the following definitions:
Single pass yield = _oles of product recovered x 100 moles of acrolein fed Conversion = moles of acrolein reacted x 130 moles of acrolein fed Selectivit m_les of acrylic acid recovered x 100 moles of acrolein reacted :~
~,,' ,.
.. - .. .
' i 7 ; ~ ' '', :, ' - ,' "', ,,, ;, . ' ' '' '. . . ' , ' ' : ' ,, , , . : . . . , . . , ,, ~ , ~; .. .. . , ,,. .,, . . ' ' .' ' : .
,.. . . . . . . ........... . . . .
.. . . . .
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.,, C~ l o ~ co a~
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.,, o o ~ ~ o o C~
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t, ~ ,~ .. ., -.
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~ ~ 3~ o o o ~o ~ ~
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o~
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o <1 :,- ' ,':
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~ .
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, . ~ , . ...
lOSS468 In the same manner as shown by the examples above, other catalysts of the invention containing thorium instead of uranium or containing different amounts of uranium or thorium and different optional elements, such as Fe, Mn, Ni, Mg and the like, are used to produce acrylic acid.
Moreover, promoted catalysts containing various amounts of tungsten, vanadium and molybdenum are used.
: Also using the catalysts of the invention, maleic anhydride, methacrylic acid or acrylates are made by known oxldation reactlons.
' ..,.
~1 ,.~, ., _ 9_ - :
, .1j 1 ~, .
., ~
.~ .
i ......... . . ~, ~. . .. ... ... . .
Claims (10)
1. The catalyst composition consisting of oxides or oxide complexes having the empirical formula A D W V Mo O
a b c d e x wherein A is Co, Fe, Ni, ZN, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is uranium, thorium or mixture thereof;
and wherein a is 0 to about 5;
b, c and d are about 0.1 to about 10;
e is a number of about 6 to about 16; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
a b c d e x wherein A is Co, Fe, Ni, ZN, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is uranium, thorium or mixture thereof;
and wherein a is 0 to about 5;
b, c and d are about 0.1 to about 10;
e is a number of about 6 to about 16; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
2. The catalyst of Claim 1 wherein more than about 50% of the atoms, exclusive of oxygen and any support material, are molybdenum.
3. The catalyst composition of Claim 1 that contains no optional components.
4. The catalyst composition of Claim 1 wherein A
if Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof and a is greater than zero.
if Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu or mixture thereof and a is greater than zero.
5. The catalyst composition of Claim 4 wherein A
is copper.
is copper.
6. The catalyst composition of Claim 4 wherein A
is cobalt.
is cobalt.
7. In the process for the production of acrylic acid or methacrylic acid from acrolein or methacrolein with molecular oxygen in the presence of steam at a temperature of about 200° to about 500°C., the improvement comprising using as the catalyst a catalyst having the empirical formula A D W V Mo O
a b c d e x wherein A is Co, Fe, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is uranium, thorium or mixture thereof;
and wherein a is 0 to about 5;
b, c and d are about 0.1 to about 10;
e is a number of about 6 to about 16; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
a b c d e x wherein A is Co, Fe, Ni, Zn, Cu, Mg, Mn, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum, an element of the lanthanoid series or mixture thereof; and D is uranium, thorium or mixture thereof;
and wherein a is 0 to about 5;
b, c and d are about 0.1 to about 10;
e is a number of about 6 to about 16; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
8. The process of claim 7 wherein acrylic acid is prepared from acrolein.
9. The process of claim 7 wherein D is uranium.
10. The process of claim 9 wherein a is 0.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42826773A | 1973-12-26 | 1973-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1055468A true CA1055468A (en) | 1979-05-29 |
Family
ID=23698187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA215,156A Expired CA1055468A (en) | 1973-12-26 | 1974-12-03 | Catalyst compositions especially useful for preparation of unsaturated acids |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5097592A (en) |
| AT (1) | AT343604B (en) |
| BE (1) | BE823871A (en) |
| BG (1) | BG31643A3 (en) |
| BR (1) | BR7410607D0 (en) |
| CA (1) | CA1055468A (en) |
| CH (1) | CH600947A5 (en) |
| CS (1) | CS212754B2 (en) |
| DD (1) | DD115652A5 (en) |
| DE (1) | DE2459092A1 (en) |
| ES (1) | ES433229A1 (en) |
| FR (1) | FR2255953B1 (en) |
| GB (1) | GB1482686A (en) |
| IN (1) | IN143815B (en) |
| IT (1) | IT1027951B (en) |
| NL (1) | NL7416801A (en) |
| NO (1) | NO142242C (en) |
| RO (1) | RO66354A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301030A (en) | 1980-08-05 | 1981-11-17 | The Standard Oil Company | Bi-containing methacrolein oxidation catalysts |
| US4301031A (en) | 1980-08-05 | 1981-11-17 | The Standard Oil Company | Methacrolein oxidation catalysts |
| JP2702864B2 (en) * | 1993-03-12 | 1998-01-26 | 株式会社日本触媒 | Catalyst regeneration method |
| DE10137534A1 (en) | 2001-08-01 | 2003-02-13 | Basf Ag | Maleic anhydride production useful as an intermediate in the production of e.g. gamma-butyrolactone, comprises the heterogeneous catalyzed gas phase oxidation of n-butene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1045704B (en) * | 1973-11-28 | 1980-06-10 | Sir Soc Italiana Resine Spa | REFINEMENTS IN THE ACRYLIC ACID PREPARATION PROCEDURE |
-
1974
- 1974-12-03 CA CA215,156A patent/CA1055468A/en not_active Expired
- 1974-12-10 NO NO744446A patent/NO142242C/en unknown
- 1974-12-13 DE DE19742459092 patent/DE2459092A1/en not_active Withdrawn
- 1974-12-17 GB GB54373/74A patent/GB1482686A/en not_active Expired
- 1974-12-19 BR BR10607/74A patent/BR7410607D0/en unknown
- 1974-12-20 IT IT30905/74A patent/IT1027951B/en active
- 1974-12-20 DD DD183277A patent/DD115652A5/xx unknown
- 1974-12-20 ES ES433229A patent/ES433229A1/en not_active Expired
- 1974-12-21 IN IN2825/CAL/74A patent/IN143815B/en unknown
- 1974-12-23 NL NL7416801A patent/NL7416801A/en not_active Application Discontinuation
- 1974-12-23 AT AT1028474A patent/AT343604B/en not_active IP Right Cessation
- 1974-12-24 FR FR7442689A patent/FR2255953B1/fr not_active Expired
- 1974-12-24 CH CH1730374A patent/CH600947A5/xx not_active IP Right Cessation
- 1974-12-25 JP JP50004149A patent/JPS5097592A/ja active Pending
- 1974-12-26 RO RO7480950A patent/RO66354A/en unknown
- 1974-12-26 BG BG028559A patent/BG31643A3/en unknown
- 1974-12-27 CS CS749041A patent/CS212754B2/en unknown
- 1974-12-27 BE BE151936A patent/BE823871A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2459092A1 (en) | 1975-07-10 |
| FR2255953A1 (en) | 1975-07-25 |
| DD115652A5 (en) | 1975-10-12 |
| JPS5097592A (en) | 1975-08-02 |
| ES433229A1 (en) | 1977-11-01 |
| ATA1028474A (en) | 1977-10-15 |
| CH600947A5 (en) | 1978-06-30 |
| NO142242B (en) | 1980-04-14 |
| BE823871A (en) | 1975-06-27 |
| IT1027951B (en) | 1978-12-20 |
| IN143815B (en) | 1978-02-11 |
| NO142242C (en) | 1980-07-23 |
| BR7410607D0 (en) | 1975-09-02 |
| NL7416801A (en) | 1975-06-30 |
| BG31643A3 (en) | 1982-02-15 |
| GB1482686A (en) | 1977-08-10 |
| AT343604B (en) | 1978-06-12 |
| RO66354A (en) | 1979-03-15 |
| FR2255953B1 (en) | 1981-12-24 |
| CS212754B2 (en) | 1982-03-26 |
| NO744446L (en) | 1975-07-21 |
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