Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid
US-9580376-B2 · Feb 28, 2017 · US
US10851040B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10851040-B2 |
| Application number | US-201716088690-A |
| Country | US |
| Kind code | B2 |
| Filing date | Mar 29, 2017 |
| Priority date | Mar 29, 2016 |
| Publication date | Dec 1, 2020 |
| Grant date | Dec 1, 2020 |
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A method for producing at least one oxidation product selected from the group consisting of acrolein and acrylic acid is provided. This method can alleviate concerns about deterioration of a gas-phase oxidation catalyst and reaction runaway in a restart period after a shutdown, and can allow the reaction to proceed in a stable state. Using a fixed-bed reactor filled with a gas-phase oxidation catalyst, at least one source gas selected from the group consisting of propylene and acrolein is subjected to a gas-phase contact oxidation reaction while a heating medium is caused to contact with or circulate through the fixed-bed reactor and thereby to heat the fixed-bed reactor. The temperature of the heating medium when the load is maximum in the restart period after the shutdown is controlled to be lower than the temperature of the heating medium when the load is maximum in an initial start-up period.
Opening claim text (preview).
The invention claimed is: 1. A method for producing at least one oxidation product selected from the group consisting of acrolein and acrylic acid, with use of a fixed-bed reactor filled with a gas-phase oxidation catalyst, by subjecting at least one source gas selected from the group consisting of propylene and acrolein to a gas-phase contact oxidation reaction while causing a heating medium to contact with or circulate through the fixed-bed reactor and thereby heating the fixed-bed reactor, wherein the temperature of the heating medium at maximum load in the restart period after a shutdown is controlled to be lower than the temperature of the heating medium at maximum load in the initial start-up period. 2. The method for producing an oxidation product according to claim 1 , wherein production of the oxidation product is restarted after the shutdown within 9000 hours after an initial start-up of the reaction. 3. The method for producing an oxidation product according to claim 1 , wherein, in the restart period after the shutdown, propylene as the source gas is subjected to the gas-phase contact oxidation reaction to produce acrolein and acrylic acid, with use of the fixed-bed reactor filled with a gas-phase oxidation catalyst which has a composition represented by following Formula (1), Mo 12 Bi a Ni b Co c Fe d X e Y f Z g O h (1) wherein Mo, Bi, Ni, Co, Fe and O represent molybdenum, bismuth, nickel, cobalt, iron and oxygen, respectively; X represents at least one element selected from the group consisting of magnesium, calcium, manganese, copper, zinc, tin, cerium and samarium; Y represents at least one element selected from the group consisting of boron, phosphorus, arsenic, antimony, tungsten, chromium and titanium; Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, thallium and cesium; a, b, c, d, e, f, g and h represent atomic ratios of the respective elements relative to 12 molybdenum atoms, wherein 0.1≤a≤7, 0.5≤b+c≤20, 0.5≤d≤8, 0≤e≤10, 0≤f≤10 and 0≤g≤0.2 and wherein h is a number determined by oxidation states of the elements except oxygen. 4. The method for producing an oxidation product according to claim 1 , wherein the fixed-bed reactor is a multistage fixed-bed reactor which is equipped with a first fixed-bed reactor filled with a first gas-phase oxidation catalyst and a second-stage fixed-bed reactor filled with a second gas-phase oxidation catalyst, the second-stage fixed-bed reactor being connected to a gas outlet side of the first-stage fixed-bed reactor, and wherein acrolein is produced in the first-stage fixed-bed reactor by a gas-phase contact oxidation reaction of propylene, and acrylic acid is produced in the second-stage fixed-bed reactor by a gas-phase contact oxidation reaction of the thus produced acrolein. 5. The method for producing an oxidation product according to claim 2 , wherein, in the restart period after the shutdown, propylene as the source gas is subjected to the gas-phase contact oxidation reaction to produce acrolein and acrylic acid, with use of the fixed-bed reactor filled with a gas-phase oxidation catalyst which has a composition represented by following Formula (1), Mo 12 Bi a Ni b Co c Fe d X e Y f Z g O h (1) wherein Mo, Bi, Ni, Co, Fe and O represent molybdenum, bismuth, nickel, cobalt, iron and oxygen, respectively; X represents at least one element selected from the group consisting of magnesium, calcium, manganese, copper, zinc, tin, cerium and samarium; Y represents at least one element selected from the group consisting of boron, phosphorus, arsenic, antimony, tungsten, chromium and titanium; Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, thallium and cesium; a, b, c, d, e, f, g and h represent atomic ratios of the respective elements relative to 12 molybdenum atoms, wherein 0.1≤a≤7, 0.5≤b+c≤20, 0.5≤d≤8, 0≤e≤10, 0≤f≤10 and 0≤g≤0.2 and wherein h is a number determined by oxidation states of the elements except oxygen. 6. The method for producing an oxidation product according to claim 2 , wherein the fixed-bed reactor is a multistage fixed-bed reactor which is equipped with a first fixed-bed reactor filled with a first gas-phase oxidation catalyst and a second-stage fixed-bed reactor filled with a second gas-phase oxidation catalyst, the second-stage fixed-bed reactor being connected to a gas outlet side of the first-stage fixed-bed reactor, and wherein acrolein is produced in the first-stage fixed-bed reactor by a gas-phase contact oxidation reaction of propylene, and acrylic acid is produced in the second-stage fixed-bed reactor by a gas-phase contact oxidation reaction of the thus produced acrolein. 7. The method for producing an oxidation product according to claim 3 , wherein the fixed-bed reactor is a multistage fixed-bed reactor which is equipped with a first fixed-bed reactor filled with a first gas-phase oxidation catalyst and a second-stage fixed-bed reactor filled with a second gas-phase oxidation catalyst, the second-stage fixed-bed reactor being connected to a gas outlet side of the first-stage fixed-bed reactor, and wherein acrolein is produced in the first-stage fixed-bed reactor by a gas-phase contact oxidation reaction of propylene, and acrylic acid is produced in the second-stage fixed-bed reactor by a gas-phase contact oxidation reaction of the thus produced acrolein. 8. The method for producing an oxidation product according to claim 5 , wherein the fixed-bed reactor is a multistage fixed-bed reactor which is equipped with a first fixed-bed reactor filled with a first gas-phase oxidation catalyst and a second-stage fixed-bed reactor filled with a second gas-phase oxidation catalyst, the second-stage fixed-bed reactor being connected to a gas outlet side of the first-stage fixed-bed reactor, and wherein acrolein is produced in the first-stage fixed-bed reactor by a gas-phase contact oxidation reaction of propylene, and acrylic acid is produced in the second-stage fixed-bed reactor by a gas-phase contact oxidation reaction of the thus produced acrolein.
characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title
in propene or isobutene · CPC title
Constitutive chemical elements of heterogeneous catalysts · CPC title
Alkali or alkaline earth metals · CPC title
of propene, butenes, acrolein or methacrolein · CPC title
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