USRE29901E - Catalyst for producing unsaturated carboxylic acids - Google Patents
Catalyst for producing unsaturated carboxylic acids Download PDFInfo
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- USRE29901E USRE29901E US05/843,351 US84335177A USRE29901E US RE29901 E USRE29901 E US RE29901E US 84335177 A US84335177 A US 84335177A US RE29901 E USRE29901 E US RE29901E
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 7
- 239000012808 vapor phase Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
- B01J23/8878—Chromium
-
- 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
- B01J23/70—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
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- B01J35/60—
-
- B01J35/612—
-
- 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
Definitions
- This invention relates to a process for producing unsaturated carboxylic acids. More specifically, the invention relates to a process for producing unsaturated carboxylic acids by catalytically oxidizing unsaturated aldehydes having not less than 3 carbon atoms in the vapor phase in the presence of a catalyst, for example, a process for producing acrylic acid from acrolein, or methacrylic acid from methacrolein.
- Examples of the conventional catalysts for use in the production of acrylic acid or methacrylic acid by the catalytic vapor phase oxidation of acrolein or methacrolein include a catalytic oxide composed of molybdenum and vanadium as disclosed in Japanese Pat. No. 1775/66, and a catalytic oxide composed of molybdenum, vanadium, aluminum and copper as disclosed in Japanese Pat. No. 26287/69.
- the specification of Japanese Pat. No. 1775/66 discloses that with the catalyst used there, the maximum one-pass yield of acrylic acid is 76.4 %. Such a yield is still unsatisfactory for commercial operation. According to the specification of Japanese Pat. No.
- the yield of acrylic acid can be 97-97.5 % at a space velocity of 500 to 1,000 hr -1 when aluminum sponge is used as a carrier and the catalyst is used in a strongly reduced condition by pretreatment (in a state where oxygen is insufficient).
- the space velocity is reduced to 2,000 hr -1 , the yield abruptly goes down to 89.5 %.
- the pretreatment for strongly reducing the catalyst includes a step of treating the catalyst with a reaction gas at a temperature higher than the reaction temperature, and therefore, various difficulties are encountered.
- an object of the present invention is to provide a process for producing unsaturated carboxylic acids which can be operated on a commercial basis using a novel catalyst.
- Oxygen in the catalytic oxide need not be present in a specially reduced condition. It is assumed that oxygen is present in the catalytic oxide in the form of a complex metal oxide or metal acid salt. Therefore, the amount of oxygen present in the catalytic oxide varies according to the atomic ratios of the metal elements that constitute the catalytic oxide.
- inert porous substances may be exemplified, or inert porous substances. Specific examples include alpha-alumina, silicon carbide, pumice, silica, zirconia, titanium oxide, or mixtures of these.
- the inert carrier that is conveniently used in the present invention has a surface area of not more than 2 m 2 /g and a porosity of 30 to 65 %, at least 90 % of the pores having a pore diameter in the range of 50 to 1,500 microns.
- the catalyst used in the present invention can be prepared for example by adding an aqueous solution of ammonium bichromate and an aqueous solution of copper nitrate to an aqueous solution containing ammonium molybdate, ammonium paratungstate, and ammonium metavanadate, pouring a carrier material into the mixture, heating the mixture to evaporate it to dryness and thereby to deposit the compounds on the carrier, if desired molding it into tablets for instance, and then calcining it at 350°-600° C. Any compound which can form a catalytic oxide by calcination such as hydroxides or carbonates can be used as materials for the production of the catalysts.
- the catalytic vapor phase oxidation process of the present invention can be performed by passing a gaseous mixture consisting of 1 to 10 % by volume of an unsaturated aldehyde (for example, acrolein, or methacrolein), 5 to 15 % by volume of molecular oxygen, 20 to 60 % by volume of steam, and 20 to 50 % by volume of an inert gas over the catalyst prepared as above described, at a temperature of 200° to 350° C. and a pressure of atmospheric pressure to 10 atmospheres.
- the space velocity is maintained at 500 to 5,000 hr -1 .
- the reaction can be carried out either in a fixed bed or in a fluidized bed.
- the one-pass yield of the unsaturated carboxylic acid can be maintained high without a decrease in the space velocity. While not wishing to be limited by any theory, it is assumed that this is perhaps because the catalytic activity is regulated by the bonding of complex oxides of copper, chromium, and tungsten or acid salts with the Mo-V system, and that it is controlled by the porosity of the carrier.
- Example 1 The procedure of Example 1 was repeated except that ammonium paratungstate, ammonium bichromate, and copper nitrate were not used. As a result a catalyst in which a catalytic oxide having a metal element composition Mo 12 V 4 .6 deposited on the alpha-alumina carrier was obtained. Using this catalyst, the reaction was performed under the same conditions as set forth in Example 1. The results are given in Table 1.
- Example 1 The procedure of Example 1 was repeated except that ammonium paratungstate and ammonium bichromate were not used. As a result a catalyst in which a catalytic oxide having a metal element composition of Mo 12 V 4 .6 Cu 2 .2 deposited on alpha-alumina was obtained. Using this catalyst, the reaction was performed under the same conditions as set forth in Example 1. The results obtained are given in Table 1.
- Example 2 Using the same catalyst as set forth in Example 1, the reaction was performed under the same conditions as in Example 1 except that the space velocity was changed to 4,000 hr -1 (Example 2) and 5,000 hr -1 (Example 3). The results are given in Table 2 below.
- Example 3 The procedure of Example 1 was repeated except that the composition of the gaseous mixture was changed. The results obtained are given in Table 3.
- Example 1 The procedure of Example 1 was repeated except that a different carrier was used. The results are given in Table 4.
- Example 2 The procedure of Example 1 was repeated except that the atomic ratio of metal elements in the catalytic oxide was varied. The results obtained are given in Table 5.
- Example 2 Using the same catalyst and apparatus as used in Example 1, a gaseous mixture consisting of 4 % by volume of methacrolein, 51 % of air, and 45 % of steam was reacted at 340° C. and a space velocity of 2,000 hr -1 .
- the conversion of methacrolein was 70 %; the selectivity of methacrylic acid was 75.5 %; and the one-pass yield of methacrylic acid was 52.8 %.
Abstract
A process for producing unsaturated carboxylic acids, which comprises oxidizing unsaturated aldehydes in the vapor phase in the presence of a catalyst comprising a catalytic oxide supported on an inert carrier, such catalytic oxide containing metal elements in the atomic ratio Mo:V:Cu:Cr:W of 12:2-14:1-6:0-4:0-12 with the proviso that Cr + W is not 0.
Description
This is a division of application Ser. No. 190,661 filed Oct. 19, 1971, now U.S. Pat. No. 3,833,649.
This invention relates to a process for producing unsaturated carboxylic acids. More specifically, the invention relates to a process for producing unsaturated carboxylic acids by catalytically oxidizing unsaturated aldehydes having not less than 3 carbon atoms in the vapor phase in the presence of a catalyst, for example, a process for producing acrylic acid from acrolein, or methacrylic acid from methacrolein.
Generally, in the commercial production of unsaturated carboxylic acids by the catalytic vapor phase oxidation of unsaturated aldehydes, it is of utmost importance to use catalysts which give high conversions of the unsaturated aldehydes and high selectivities to unsaturated carboxylic acids. It is required that the catalysts should be very easily produced on a commercial basis and have stability over prolonged periods of time.
Examples of the conventional catalysts for use in the production of acrylic acid or methacrylic acid by the catalytic vapor phase oxidation of acrolein or methacrolein include a catalytic oxide composed of molybdenum and vanadium as disclosed in Japanese Pat. No. 1775/66, and a catalytic oxide composed of molybdenum, vanadium, aluminum and copper as disclosed in Japanese Pat. No. 26287/69. The specification of Japanese Pat. No. 1775/66 discloses that with the catalyst used there, the maximum one-pass yield of acrylic acid is 76.4 %. Such a yield is still unsatisfactory for commercial operation. According to the specification of Japanese Pat. No. 26287/69, the yield of acrylic acid can be 97-97.5 % at a space velocity of 500 to 1,000 hr-1 when aluminum sponge is used as a carrier and the catalyst is used in a strongly reduced condition by pretreatment (in a state where oxygen is insufficient). However, when the space velocity is reduced to 2,000 hr-1, the yield abruptly goes down to 89.5 %. In addition, the pretreatment for strongly reducing the catalyst includes a step of treating the catalyst with a reaction gas at a temperature higher than the reaction temperature, and therefore, various difficulties are encountered.
Accordingly, an object of the present invention is to provide a process for producing unsaturated carboxylic acids which can be operated on a commercial basis using a novel catalyst.
It has now been found that by using a catalytic oxide comprising molybdenum, vanadium, copper, chromium, and/or tungsten, and oxygen supported on an inert carrier, unsaturated carboxylic acids, for example acrylic acid or methacrylic acid can be obtained in very high one-pass yields from unsaturated aldehydes, for example acrolein or methacrolein, and the above object of the present invention can be achieved.
The catalytic oxide used in the present invention is characterized in that the metallic elements which constitute it are present in the following atomic ratios: Mo:V:Cu:Cr:W = 12.2-14:1-6:0-4:0-12 (with the proviso Cr + W ≠ O). Oxygen in the catalytic oxide need not be present in a specially reduced condition. It is assumed that oxygen is present in the catalytic oxide in the form of a complex metal oxide or metal acid salt. Therefore, the amount of oxygen present in the catalytic oxide varies according to the atomic ratios of the metal elements that constitute the catalytic oxide.
As the inert carrier for supporting the catalytic oxide in the present invention, natural, inert porous substances may be exemplified, or inert porous substances. Specific examples include alpha-alumina, silicon carbide, pumice, silica, zirconia, titanium oxide, or mixtures of these. The inert carrier that is conveniently used in the present invention has a surface area of not more than 2 m2 /g and a porosity of 30 to 65 %, at least 90 % of the pores having a pore diameter in the range of 50 to 1,500 microns.
The catalyst used in the present invention can be prepared for example by adding an aqueous solution of ammonium bichromate and an aqueous solution of copper nitrate to an aqueous solution containing ammonium molybdate, ammonium paratungstate, and ammonium metavanadate, pouring a carrier material into the mixture, heating the mixture to evaporate it to dryness and thereby to deposit the compounds on the carrier, if desired molding it into tablets for instance, and then calcining it at 350°-600° C. Any compound which can form a catalytic oxide by calcination such as hydroxides or carbonates can be used as materials for the production of the catalysts.
The catalytic vapor phase oxidation process of the present invention can be performed by passing a gaseous mixture consisting of 1 to 10 % by volume of an unsaturated aldehyde (for example, acrolein, or methacrolein), 5 to 15 % by volume of molecular oxygen, 20 to 60 % by volume of steam, and 20 to 50 % by volume of an inert gas over the catalyst prepared as above described, at a temperature of 200° to 350° C. and a pressure of atmospheric pressure to 10 atmospheres. The space velocity is maintained at 500 to 5,000 hr-1. The reaction can be carried out either in a fixed bed or in a fluidized bed.
According to the present invention, the one-pass yield of the unsaturated carboxylic acid can be maintained high without a decrease in the space velocity. While not wishing to be limited by any theory, it is assumed that this is perhaps because the catalytic activity is regulated by the bonding of complex oxides of copper, chromium, and tungsten or acid salts with the Mo-V system, and that it is controlled by the porosity of the carrier.
The invention will be described in detail by the following Examples and Comparative Examples which are presented for illustrative, rather than limitative, purposes.
The conversion, selectivity, and one-pass yield used in the present specification and claims are defined as follows: ##EQU1##
While 5,000 ml. of water were being heated with stirring, 104 g of ammonium paratungstate, 86 9 of ammonium metavanadate, 338 g of ammonium molybdate, and 12 g of ammonium bichromate were added to the water. Separately, an aqueous solution of 86 g of copper nitrate in 300 ml. of water was prepared, and mixed with the aqueous solution obtained above. The mixed solution obtained was put into a porcelain evaporator on a warm bath, and 1,000 ml. of particulate alpha-alumina having a diameter of 3 to 5 mm (surface area 1 m2 /g or less, porosity 42 %, and 92 % of the pores being of a pore diameter 75-250 microns) were added as a carrier. With stirring, the mixture was evaporated to dryness to deposit the compounds on the carrier, and then calcined for 5 hours at 400° C. As a result a catalyst in which a catalytic oxide having a metal element composition of Mo12 V4.6 Cu2.2 Cr0.6 W2.4 deposited on the alpha-alumina carrier was obtained.
One thousand milliliters of the resulting catalyst were packed into a U-shaped stainless steel tube having a diameter of 25 cm, and the tube was immersed in a molten nitrate bath heated at 220°-260° C. A gaseous mixture consisting of 4 % acrolein, 55 % of air, and 41 % of steam, all by volume, was fed into the tube, and reacted at a space velocity of 1,000 to 3,000 hr-1. The results obtained are shown in Table 1.
The procedure of Example 1 was repeated except that ammonium paratungstate, ammonium bichromate, and copper nitrate were not used. As a result a catalyst in which a catalytic oxide having a metal element composition Mo12 V4.6 deposited on the alpha-alumina carrier was obtained. Using this catalyst, the reaction was performed under the same conditions as set forth in Example 1. The results are given in Table 1.
The procedure of Example 1 was repeated except that ammonium paratungstate and ammonium bichromate were not used. As a result a catalyst in which a catalytic oxide having a metal element composition of Mo12 V4.6 Cu2.2 deposited on alpha-alumina was obtained. Using this catalyst, the reaction was performed under the same conditions as set forth in Example 1. The results obtained are given in Table 1.
Table 1
__________________________________________________________________________
Atomic ratio of Reaction Acrolein
Acrylic
Acrylic acid
metal elements in
temper-
Space
conver-
acid one-pass
catalytic oxide ature
velocity
sion selectivity
yield
Mo V Cu
Cr
W (° C.)
(hr.sup.-1)
(mol %)
(mol %)
(mol %)
__________________________________________________________________________
Example 1
12 4.6
2.2
0.6
2.4
220 1000 100 98.0 98.0
240 2000 99.5 98.0 97.5
260 3000 99.0 98.2 97.2
Compara-
12 4.6
0 0 0 220 1000 49.5 40.0 19.8
tive 240 2000 45.0 46.5 20.9
Example 1 260 3000 38.0 51.0 19.4
Compara-
12 4.6
2.2
0 0 220 1000 54.6 92.0 50.2
tive 240 2000 46.3 93.0 43.1
Example 2 260 3000 40.0 93.0 37.2
__________________________________________________________________________
Using the same catalyst as set forth in Example 1, the reaction was performed under the same conditions as in Example 1 except that the space velocity was changed to 4,000 hr-1 (Example 2) and 5,000 hr-1 (Example 3). The results are given in Table 2 below.
Table 2
__________________________________________________________________________
Space
Reaction
Conversion
Selectivity
One-pass yield
velocity
temperature
of acrolein
of acrylic
of acrylic
Examples
(hr.sup.-1)
(° C.)
(mol %)
acid (mol %)
acid (mol %)
__________________________________________________________________________
2 4000 270 98.5 98 96.5
3 5000 270 97.0 97.8 9.4
__________________________________________________________________________
The procedure of Example 1 was repeated except that the composition of the gaseous mixture was changed. The results obtained are given in Table 3.
Table 3
__________________________________________________________________________
Compositon of Reaction Conver-
Selectivity
One-pass
gaseous mixture temper-
Space
sion of
of acrylic
yield of
(vol. %) ature
velocity
acrolein
acid acrylic acid
Examples
Acrolein
Air
Steam
(° C.)
(hr.sup.-1)
(mol %)
(mol %)
(mol %)
__________________________________________________________________________
4 5 55 40 270 4000 98.0 97.7 95.8
5 6 54 40 265 3000 99.0 97.0 96.0
6 8 62 30 265 3000 98.5 96.1 94.7
__________________________________________________________________________
The procedure of Example 1 was repeated except that a different carrier was used. The results are given in Table 4.
Table 4
__________________________________________________________________________
Physical properties
Reaction Conver-
Selectivity
One-pass
of the carrier temper-
Space
sion of
of acrylic
yield of
Surface Pore ature
velocity
acrolein
acid acrylic acid
Example
Carrier
area Porosity
distribution
(° C.)
(hr.sup.-1)
(mol %)
(mol %)
(mol %)
__________________________________________________________________________
7 Silcon
less than
55% 75-500μ
230 2000 99.0 98.0 97.0
carbide
1 m.sup.2 /g
93%
8 α-alumina
less than
47% 75-1000μ
230 2000 99.0 98.0 97.0
(50%) 1 m.sup.2 /g
95%
Sillicon
carbide
9 α-alumina
less than
40% 50-1200μ
230 2000 100 98.0 98.0
(75%) 1 m.sup.2 /g
95%
Silica
__________________________________________________________________________
The procedure of Example 1 was repeated except that the atomic ratio of metal elements in the catalytic oxide was varied. The results obtained are given in Table 5.
Table 5
__________________________________________________________________________
Atomic ratio of Reaction Conver-
Selectivity
One-pass
metal elements in
temper-
Space
sion of
of acrylic
yield of
the catalytic oxide
ature
velocity
acrolein
acid acrylic acid
Example
No V Cu
Cr
W (° C.)
(hr.sup.-1)
(mol %)
(mol %)
(mol %)
__________________________________________________________________________
10 12 6 2.2
0 2.4
240 2000 99.0 98.0 97.0
11 12 4.6
2.2
0.4
4 250 2000 98.0 97.5 95.6
12 12 6 2.2
1.2
0 240 2000 99.5 98.0 97.5
13 12 4.6
4.4
0.6
2.4
240 2000 98.5 98.0 96.5
14 12 8 2.2
0.8
1.0
230 2000 100 97.5 97.5
__________________________________________________________________________
The results obtained in Examples 1 to 14 above demonstrate that the reaction can be performed under a wide range of conditions without reducing the yield of acrylic acid.
Using the same catalyst and apparatus as used in Example 1, a gaseous mixture consisting of 4 % by volume of methacrolein, 51 % of air, and 45 % of steam was reacted at 340° C. and a space velocity of 2,000 hr-1. The conversion of methacrolein was 70 %; the selectivity of methacrylic acid was 75.5 %; and the one-pass yield of methacrylic acid was 52.8 %.
Claims (8)
1. A catalyst adapted for the production of unsaturated carboxylic acids through the vapor phase oxidation of unsaturated aldehydes comprising a catalytic oxide supported on an inert carrier, said catalytic oxide consisting essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of 12:2-14:1-6:0-4:0-12 with the proviso that Cr + W is not O, said inert carrier having a surface area not greater than 2 m2 /g and a porosity of 30 to 65%, at least 90% of the pores having a pore diameter in the range of 50 to 1,500 microns.
2. The catalyst of claim 1 wherein said inert carrier is selected from α-alumina, silicon carbide, pumice, silica, zirconia, titanium oxide and mixtures thereof.
3. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:4:6:2.2:0.6:2.4.
4. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:6:2.2:0:2.4.
5. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:4.6:2.2.0.4:4.
6. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:6:2.2:1.2:0.
7. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:4.6:4.4:0.6:2.4.
8. The catalyst of claim 1 wherein said catalytic oxide consists essentially of the recited metal elements in the atomic ratio Mo:V:Cu:Cr:W of about 12:8:2.2:0.8:1.0.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45092759A JPS4911371B1 (en) | 1970-10-23 | 1970-10-23 | |
| JP45-92759 | 1970-10-23 | ||
| US396474A US3886092A (en) | 1971-10-19 | 1973-09-12 | Process for producing unsaturated carboxylic acids |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00190661A Division US3833649A (en) | 1970-10-23 | 1971-10-19 | Process for producing unsaturated carboxylic acids |
| US396474A Reissue US3886092A (en) | 1970-10-23 | 1973-09-12 | Process for producing unsaturated carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29901E true USRE29901E (en) | 1979-02-06 |
Family
ID=26434133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/843,351 Expired - Lifetime USRE29901E (en) | 1970-10-23 | 1977-10-18 | Catalyst for producing unsaturated carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29901E (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695668A (en) | 1986-03-24 | 1987-09-22 | The Standard Oil Company | Molybdenum-tungsten-containing catalyst and methane conversion process using same |
| US4808563A (en) | 1986-03-24 | 1989-02-28 | The Standard Oil Company | Molybdenum-tungsten-containing catalyst for methane conversion process |
| US5739392A (en) * | 1994-11-14 | 1998-04-14 | Nippon Shokubai Co., Ltd. | Process for production of acrylic acid |
| US6429332B1 (en) | 1994-05-31 | 2002-08-06 | Nippon Shokubai Co., Ltd. | Catalyst for production of acrylic acid and method for production of acrylic acid by the use of the catalyst |
| US6638890B2 (en) * | 1999-12-08 | 2003-10-28 | Nippon Shokubai Co. Ltd. | Modified carrier, complex oxide catalyst and process for preparation of acrylic acid |
| US20040176641A1 (en) * | 2003-02-27 | 2004-09-09 | Nippon Shokubai Co., Ltd. | Composite-oxide catalyst and process for production of acrylic acid using said catalyst |
| US20040245681A1 (en) * | 2003-06-04 | 2004-12-09 | Basf Aktiengesellschaft | Thermal treatment of the precursor material of a catalytically active material |
| US20040249183A1 (en) * | 2003-06-04 | 2004-12-09 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
| US20060245992A1 (en) * | 2001-01-25 | 2006-11-02 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3435069A (en) * | 1960-04-14 | 1969-03-25 | Distillers Co Yeast Ltd | Oxidation of acrolein and methacrolein with a molybdenum polyvalent metaloxygen catalyst |
| US3567772A (en) * | 1966-03-30 | 1971-03-02 | Toa Gosei Chem Ind | Process for the production of acrylic acid |
| US3644509A (en) * | 1969-02-03 | 1972-02-22 | Celanese Corp | Oxidation of unsaturated aldehydes to the corresponding acids |
| US3736354A (en) * | 1968-05-13 | 1973-05-29 | Rikagaku Kenkyusho | Process for the production of acrylic acid |
| US3775474A (en) * | 1971-04-27 | 1973-11-27 | Nippon Catalytic Chem Ind | Process for the preparation of acrylic acid |
-
1977
- 1977-10-18 US US05/843,351 patent/USRE29901E/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3435069A (en) * | 1960-04-14 | 1969-03-25 | Distillers Co Yeast Ltd | Oxidation of acrolein and methacrolein with a molybdenum polyvalent metaloxygen catalyst |
| US3567772A (en) * | 1966-03-30 | 1971-03-02 | Toa Gosei Chem Ind | Process for the production of acrylic acid |
| US3736354A (en) * | 1968-05-13 | 1973-05-29 | Rikagaku Kenkyusho | Process for the production of acrylic acid |
| US3644509A (en) * | 1969-02-03 | 1972-02-22 | Celanese Corp | Oxidation of unsaturated aldehydes to the corresponding acids |
| US3775474A (en) * | 1971-04-27 | 1973-11-27 | Nippon Catalytic Chem Ind | Process for the preparation of acrylic acid |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808563A (en) | 1986-03-24 | 1989-02-28 | The Standard Oil Company | Molybdenum-tungsten-containing catalyst for methane conversion process |
| US4695668A (en) | 1986-03-24 | 1987-09-22 | The Standard Oil Company | Molybdenum-tungsten-containing catalyst and methane conversion process using same |
| US6429332B1 (en) | 1994-05-31 | 2002-08-06 | Nippon Shokubai Co., Ltd. | Catalyst for production of acrylic acid and method for production of acrylic acid by the use of the catalyst |
| US5739392A (en) * | 1994-11-14 | 1998-04-14 | Nippon Shokubai Co., Ltd. | Process for production of acrylic acid |
| US6638890B2 (en) * | 1999-12-08 | 2003-10-28 | Nippon Shokubai Co. Ltd. | Modified carrier, complex oxide catalyst and process for preparation of acrylic acid |
| US20060245992A1 (en) * | 2001-01-25 | 2006-11-02 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
| US7850928B2 (en) | 2001-01-25 | 2010-12-14 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
| US7429678B2 (en) | 2003-02-27 | 2008-09-30 | Nippon Shokubai Co., Ltd. | Composite-oxide catalyst and process for production of acrylic acid using said catalyst |
| US20040176641A1 (en) * | 2003-02-27 | 2004-09-09 | Nippon Shokubai Co., Ltd. | Composite-oxide catalyst and process for production of acrylic acid using said catalyst |
| US20040249183A1 (en) * | 2003-06-04 | 2004-12-09 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
| US20040245681A1 (en) * | 2003-06-04 | 2004-12-09 | Basf Aktiengesellschaft | Thermal treatment of the precursor material of a catalytically active material |
| US7524792B2 (en) * | 2003-06-04 | 2009-04-28 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
| US7589046B2 (en) * | 2003-06-04 | 2009-09-15 | Basf Aktiengesellschaft | Thermal treatment of the precursor material of a catalytically active material |
| US20090234159A1 (en) * | 2003-06-04 | 2009-09-17 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements nb and w and the elements mo, v and cu |
| US7667073B2 (en) | 2003-06-04 | 2010-02-23 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
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