WO1996032193A1 - Process for the regeneration of a catalyst - Google Patents
Process for the regeneration of a catalyst Download PDFInfo
- Publication number
- WO1996032193A1 WO1996032193A1 PCT/US1996/004635 US9604635W WO9632193A1 WO 1996032193 A1 WO1996032193 A1 WO 1996032193A1 US 9604635 W US9604635 W US 9604635W WO 9632193 A1 WO9632193 A1 WO 9632193A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- steam
- recited
- per
- maleic anhydride
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008929 regeneration Effects 0.000 title claims description 16
- 238000011069 regeneration method Methods 0.000 title claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001273 butane Substances 0.000 abstract description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 13
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- 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
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
-
- 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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a process for the regeneration of a catalyst used in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms in a reactor, particularly in a fluidized bed reactor, when the activity of the catalyst has decreased during use.
- maleic anhydride is prepared by oxidizing a hydrocarbon having four carbon atoms using a vanadium - phosphorus oxide catalyst, often called a V-P-O catalyst.
- a problem is that the catalytic activity decreases with time. Then, if the reaction temperature is raised to maintain the same level of conversion, the yield of maleic anhydride decreases. Accordingly, various processes have been tried for the regeneration of the catalyst. For example, one method to improve the catalytic activity is by means of the addition of phosphorus compounds. In JP Publication No.
- Hei-5-42436/1993 there is disclosed a process for the preparation of maleic anhydride by means of the continuous oxidation of butane in a gaseous phase wherein 0.1 to 100,000 wt.% of a phosphorus compound and 0.1 to 4 wt.% of water based on the feed are brought into contact with the catalyst during the reaction.
- other processes are known, such as a process in which a phosphorus compound and water are supplied together in situ to get the catalyst partly reactivated (U.S. Patent No. 4,701 ,433) and a steam regeneration process for a V-P-O catalyst which is treated with phosphorus (JP Publication No. Hei-4-
- JP Application Laid-Open No. Hei-5-43567/1993 discloses a regeneration process for the catalyst in which the catalyst is taken out of a reactor and then treated.
- the catalyst is treated with air at a humidity of 60% and 20 °C for 30 minutes or with a nitrogen stream saturated with water at 20 °C for one hour.
- a purpose of the present invention is to provide an improved process for the efficient regeneration of a V-P-O type catalyst.
- the present invention provides a process for the regeneration of a catalyst used in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms, wherein the catalyst comprises oxide compounds of vanadium and phosphorus, characterized in that the maleic anhydride reaction is terminated and the catalyst is then brought into contact with steam in an amount of 0.02 to 30g per g of the catalyst at 300 to 600°C.
- the catalyst used in the invention comprises oxide compounds of vanadium and phosphorus, hereinafter referred to as a V-P-O catalyst, where the activity of the catalyst has decreased during use.
- the catalyst contains crystalline vanadium - phosphorus mixed oxides as an active component where an atomic ratio of phosphorus to vanadium (P/V) is preferably 0.8 to 2.0 /1 , more preferably 1 to 1.5 /1.
- P/V atomic ratio of phosphorus to vanadium
- one such catalyst has a main crystalline component of divanad ⁇ l pyrophosphate.
- the catalyst may or may not contain carriers such as SiO 2 , A1 2 O 3 , and TiO 2 .
- the catalyst may also contain elements such as Li, B, Si, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Sn, Hf and Bi as a co-catalyst component.
- V-P-O catalysts may be prepared by known methods, for example, a method where a catalyst precursor is prepared by reducing divanadium pentaoxide with hydrochloric acid, oxalic acid, hydrazine, etc. in the presence of phosphoric acid, which is then calcined (JP Application Laid-Open No. Sho-54-120273/1979 and USP No.
- the aforesaid V-P-O type catalyst is brought into contact with steam in specific conditions when the maleic anhydride reaction has been terminated or after the catalyst has been removed from the reactor.
- the present regeneration process is carried out at a temperature of at least 300°C, preferably at least 400°C, and at most 600°C, preferably at most 550 °C. If the temperature is too low, the effect of the regeneration is reduced. If the temperature is too high, the catalyst changes in quality, so that there is a danger that the yield of maleic anhydride will decrease.
- Pressure is not restricted, but is usually at least atmospheric pressure (about 0.1 MPa), and preferably 0.1 to 0.5 MPa.
- the total amount of steam to be brought into contact with the catalyst is at least 0.02 g, preferably at least 0.2 g, more preferably at least 0.3 g, and at most 30 g, preferably at most 10 g, more preferably at most 7 g, per g of the catalyst. If the total amount of steam is too high, the catalyst tends to deteriorate.
- the rate of supplying steam is preferably at least 0.001 g/hour, more preferably at least 0.010 g/hour, and preferably at most 1 g/hour, more preferably at most 0.5g/hour, particularly at most 0.4g/hour, per g of the catalyst.
- the rate of supplying steam is too low, it is necessary to treat the catalyst for a long time, which tends to cause deterioration of the catalyst. If the rate of supplying steam is too high, the catalyst tends to deteriorate because the catalyst is treated with a consequent large amount of steam at once. Steam to be brought into contact with the catalyst may be supplied alone or it may be supplied together with other gases. If an oxidizing gas is used together with the steam, quadrivalent vanadium is often oxidized to change the structure of the divanadyl pyrophosphate crystals changed due to the high temperature in the treatment, which causes the yield of maleic anhydride to decrease.
- a reducing gas is used, quadrivalent vanadium is often reduced which also changes the structure of the divanadyl pyrophosphate crystals which also causes the yield of maleic anhydride to decrease.
- Nitrogen, carbon dioxide and rare gases such as He, Ne, Ar, etc. are preferably used. It is preferred to supply steam in the form of a mixture with at least one gas selected from the above gases.
- the concentration of steam in the gas mixture is preferably at least 5 mole%, more preferably at least 10 mole%, and preferably at most 80 mole%, more preferably at most 60 mole%.
- Steam is preferably supplied as a gas mixture with nitrogen, more preferably at a steam concentration of 5 to 80 mole%.
- the time period of the treatment with steam is not restricted as long as the above conditions are satisfied, but is preferably at least 2 hours, more preferably at least 10 hours.
- the treatment for too long a time might cause the catalyst to change in quality it is conducted preferably for at most 90 hours and more preferably at most 50 hours.
- a sample used was a V-P-O catalyst which had been used for about two years in a fluidized bed reactor in a system where n-butane was air oxidized to prepare maleic anhydride, whereby the activity of the catalyst was reduced.
- Comparison Example 9 the same amount of steam as used as in Example 3 was brought into contact with the catalyst. However, steam was supplied to the catalyst while the maleic anhydride reaction was still being carried out in contrast with Example 3. As a result, both the conversion to butane and the yield of MAH in Comparison Example 9 are lower than those in Example 3.
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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)
- Catalysts (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process is provided for regenerating a vanadium-phosphorus oxide catalyst which is used in a process for the preparation of maleic anhydride by oxidizing butane. The reaction is terminated and the catalyst is brought into contact with steam in tne amount of 0.02 to 30 g per g of catalyst at 300 to 600 °C.
Description
Process for the Regeneration of a Catalyst
The present invention relates to a process for the regeneration of a catalyst used in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms in a reactor, particularly in a fluidized bed reactor, when the activity of the catalyst has decreased during use.
Background of the Invention
It has been known that maleic anhydride is prepared by oxidizing a hydrocarbon having four carbon atoms using a vanadium - phosphorus oxide catalyst, often called a V-P-O catalyst. In this process, a problem is that the catalytic activity decreases with time. Then, if the reaction temperature is raised to maintain the same level of conversion, the yield of maleic anhydride decreases. Accordingly, various processes have been tried for the regeneration of the catalyst. For example, one method to improve the catalytic activity is by means of the addition of phosphorus compounds. In JP Publication No. Hei-5-42436/1993, there is disclosed a process for the preparation of maleic anhydride by means of the continuous oxidation of butane in a gaseous phase wherein 0.1 to 100,000 wt.% of a phosphorus compound and 0.1 to 4 wt.% of water based on the feed are brought into contact with the catalyst during the reaction. In addition, other processes are known, such as a process in which a phosphorus compound and water are supplied together in situ to get the catalyst partly reactivated (U.S. Patent No. 4,701 ,433) and a steam regeneration process for a V-P-O catalyst which is treated with phosphorus (JP Publication No. Hei-4-
75060/1992).
Also, JP Application Laid-Open No. Hei-5-43567/1993 discloses a regeneration process for the catalyst in which the catalyst is taken out of a reactor and then treated. In the examples, the catalyst is treated
with air at a humidity of 60% and 20 °C for 30 minutes or with a nitrogen stream saturated with water at 20 °C for one hour.
Summary of the Invention
A purpose of the present invention is to provide an improved process for the efficient regeneration of a V-P-O type catalyst. The present invention provides a process for the regeneration of a catalyst used in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms, wherein the catalyst comprises oxide compounds of vanadium and phosphorus, characterized in that the maleic anhydride reaction is terminated and the catalyst is then brought into contact with steam in an amount of 0.02 to 30g per g of the catalyst at 300 to 600°C.
Description of the Preferred Embodiments
The catalyst used in the invention comprises oxide compounds of vanadium and phosphorus, hereinafter referred to as a V-P-O catalyst, where the activity of the catalyst has decreased during use. The catalyst contains crystalline vanadium - phosphorus mixed oxides as an active component where an atomic ratio of phosphorus to vanadium (P/V) is preferably 0.8 to 2.0 /1 , more preferably 1 to 1.5 /1. For example, one such catalyst has a main crystalline component of divanadγl pyrophosphate. The catalyst may or may not contain carriers such as SiO2, A12O3, and TiO2. In addition, the catalyst may also contain elements such as Li, B, Si, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Sn, Hf and Bi as a co-catalyst component. These V-P-O catalysts may be prepared by known methods, for example, a method where a catalyst precursor is prepared by reducing divanadium pentaoxide with hydrochloric acid, oxalic acid, hydrazine, etc. in the presence of phosphoric acid, which is then calcined (JP Application Laid-Open No. Sho-54-120273/1979 and USP No.
4,085,122); and a method where divanadium pentaoxide is reduced in a substantially anhydrous organic solvent, which is then heated in the presence of phosphoric acid to obtain a precursor which is then calcined (JP Publication Sho-57-8761/1982 and JP Publication Hei-1- 50455/1989).
In the present process for the regeneration of a catalyst, the aforesaid V-P-O type catalyst is brought into contact with steam in specific conditions when the maleic anhydride reaction has been terminated or after the catalyst has been removed from the reactor. The present regeneration process is carried out at a temperature of at least 300°C, preferably at least 400°C, and at most 600°C, preferably at most 550 °C. If the temperature is too low, the effect of the regeneration is reduced. If the temperature is too high, the catalyst changes in quality, so that there is a danger that the yield of maleic anhydride will decrease. Pressure is not restricted, but is usually at least atmospheric pressure (about 0.1 MPa), and preferably 0.1 to 0.5 MPa. The total amount of steam to be brought into contact with the catalyst is at least 0.02 g, preferably at least 0.2 g, more preferably at least 0.3 g, and at most 30 g, preferably at most 10 g, more preferably at most 7 g, per g of the catalyst. If the total amount of steam is too high, the catalyst tends to deteriorate. The rate of supplying steam is preferably at least 0.001 g/hour, more preferably at least 0.010 g/hour, and preferably at most 1 g/hour, more preferably at most 0.5g/hour, particularly at most 0.4g/hour, per g of the catalyst. If the rate of supplying steam is too low, it is necessary to treat the catalyst for a long time, which tends to cause deterioration of the catalyst. If the rate of supplying steam is too high, the catalyst tends to deteriorate because the catalyst is treated with a consequent large amount of steam at once. Steam to be brought into contact with the catalyst may be supplied alone or it may be supplied together with other gases. If an
oxidizing gas is used together with the steam, quadrivalent vanadium is often oxidized to change the structure of the divanadyl pyrophosphate crystals changed due to the high temperature in the treatment, which causes the yield of maleic anhydride to decrease. Also a reducing gas is used, quadrivalent vanadium is often reduced which also changes the structure of the divanadyl pyrophosphate crystals which also causes the yield of maleic anhydride to decrease. Nitrogen, carbon dioxide and rare gases such as He, Ne, Ar, etc. are preferably used. It is preferred to supply steam in the form of a mixture with at least one gas selected from the above gases. The concentration of steam in the gas mixture is preferably at least 5 mole%, more preferably at least 10 mole%, and preferably at most 80 mole%, more preferably at most 60 mole%. Steam is preferably supplied as a gas mixture with nitrogen, more preferably at a steam concentration of 5 to 80 mole%. The time period of the treatment with steam is not restricted as long as the above conditions are satisfied, but is preferably at least 2 hours, more preferably at least 10 hours. As the treatment for too long a time might cause the catalyst to change in quality, it is conducted preferably for at most 90 hours and more preferably at most 50 hours.
The present invention is illustrated more specifically by means of the following examples. In the examples, the conversion to butane and the yield of maleic anhydride (MAH) are determined as follows: Conversion to butane = (molar concentration of butane at the inlet of the reactor minus molar concentration of butane at the outlet of the reactor) ÷ (molar concentration of butane at the inlet of the reactor) x 100
Yield of MAH = (moles of MAH generated per unit time) ÷ (moles of butane consumed in the reaction per unit time) x 100
Comparison Example 1
A sample used was a V-P-O catalyst which had been used for about two years in a fluidized bed reactor in a system where n-butane was air oxidized to prepare maleic anhydride, whereby the activity of the catalyst was reduced.
In order to conduct the activity test, 1 g of the catalyst sample was packed in a fixed bed flow system reactor. The reaction was then carried out, where n-butane was air oxidized to prepare maleic anhydride. The reaction conditions were as follows:
Pressure 1 atm.
Gas Hourly Space Velocity 1500 hr."1
Temperature 430 °C
Concentration of n-butane in air 1.5 mole%
Normal butane concentrations in the inlet gas and the outlet gas of the reactor were determined quantitatively with gas chromatography to find a conversion to butane of 52 mole%. The resultant MAH was absorbed in water by introducing the outlet gas in 30 to 100 ml of water for 30 to 60 minutes, which was then titrated with an aqueous 0.1 N sodium hydroxide solution to obtain the yield of MAH. As a result, the yield of
MAH was 33 mole%. Example 1
One gram of the same catalyst sample as used in Comparison Example 1 was regenerated as follows: The catalyst was packed in the same fixed bed flow system reactor as used in Comparison Example 1 , to which a gas mixture containing steam and nitrogen at a molar ratio of 1 : 1 was supplied under atmospheric pressure at the treating temperature of 430°C for 24 hours so as to supply steam to the catalyst at a rate of 0.132 g/hour per g of the catalyst.
After the regeneration treatment of the catalyst, its activity was determined in the same reactor and under the same conditions as in Comparison Example 1 to obtain a conversion to butane of 71 mole% and a yield of MAH of 42 mole%. Examples 2 - 6 and Comparison Examples 2 - 8
One gram of the same catalyst sample as used in Comparison Example 1 was regenerated as in Example 1 , except that the conditions for regeneration of the catalyst were changed as shown in the following Table 1 . After the regeneration treatment of the catalyst, its activity was determined in the same reactor and under the same conditions as in Comparison Example 1. The results are also shown in Table 1.
One gram of the same catalyst sample as used in Comparison Example 1 was regenerated, the catalyst was packed in the same fixed bed flow system reactor as used in Comparison Example 1 . A gas mixture of n-butane in air was passed through the bed at atmospheric pressure to produce maleic anhydride at a butane concentration of 1.5 mole %, a temperature of 430 °C, and a GHSV of 1500 hour"1. After 5 hours elapsed, the reaction was terminated and water was introduced into the reactor at a rate of 0.05 g/hour per g of the catalyst for 8 hours. The total amount of steam added to the catalyst was 0.4 g/ g catalyst. The water vaporized completely in a heating zone in the upper part of the catalyst bed, the upstream side.
After the regeneration treatment of the catalyst, its activity was determined in the same reactor and under the same conditions as in Comparison Example 2 resulting in the conversion to butane of 57 mole % and the yield of MAH of 35 mole %.
In Comparison Example 9, the same amount of steam as used as in Example 3 was brought into contact with the catalyst. However, steam was supplied to the catalyst while the maleic anhydride reaction was still being carried out in contrast with Example 3. As a result, both the conversion to butane and the yield of MAH in Comparison Example 9 are lower than those in Example 3.
According to the invention, it is possible to effectively regenerate a catalyst which comprises vanadium - phosphorus oxide compounds. When the catalyst which is regenerated according to the present process is packed in a fluidized bed reactor to carry out the reaction, the flowability of the catalyst is improved as well as the activity.
Claims
1. A process for the regeneration of a catalyst in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms and wherein the catalyst comprises vanadium- phosphorus oxide compounds comprising the steps of terminating the maleic anhydride reaction and contacting said catalyst with steam in the amount of 0.02 to 30 g per g of catalyst at 300 to 600°C.
2. A process as recited in claim 1 wherein the amount of said steam is 0.3 to 7 g per g of said catalyst.
3. A process as recited in claim 1 wherein said steam is contacted with said catalyst at a rate of at least 0.001 g per hour per g of catalyst.
4. A process as recited in claim 2 wherein said steam is contacted with said catalyst at a rate of at least 0.001 g per hour per g of catalyst.
5. A process as recited in claim 1 wherein said steam is contacted with said catalyst at a rate of 0.001 to 1.0 g per hour per g of catalyst.
6. A process as recited in claim 2 wherein said steam is contacted with said catalyst at a rate of 0.001 to 1.0 g per hour per g of catalyst.
7. A process as recited in claim 1 wherein a gas selected from nitrogen, carbon dioxide and rare gases is mixed with said steam.
8. A process as recited in claim 2 wherein a gas selected from nitrogen, carbon dioxide and rare gases is mixed with said steam.
9. A process as recited in claim 3 wherein a gas selected from nitrogen, carbon dioxide and rare gases is mixed with said steam.
10. A process as recited in claim 4 wherein a gas selected from nitrogen, carbon dioxide and rare gases is mixed with said steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU53849/96A AU5384996A (en) | 1995-04-14 | 1996-04-04 | Process for the regeneration of a catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7113613A JPH08332387A (en) | 1995-04-14 | 1995-04-14 | Catalyst regenerating method |
| JP7/113613 | 1995-04-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996032193A1 true WO1996032193A1 (en) | 1996-10-17 |
Family
ID=14616663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1996/004635 WO1996032193A1 (en) | 1995-04-14 | 1996-04-04 | Process for the regeneration of a catalyst |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH08332387A (en) |
| AU (1) | AU5384996A (en) |
| WO (1) | WO1996032193A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11351523B2 (en) * | 2016-09-22 | 2022-06-07 | Johnson Matthey Davy Technologies Limited | Process for regenerating a deactivated vanadium-titanium-phosphorous catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004062798A1 (en) | 2003-01-09 | 2004-07-29 | Mitsubishi Rayon Co., Ltd. | Method for preserving catalyst |
| MY146286A (en) | 2005-08-22 | 2012-07-31 | Siemens Industry Inc | An assembly for water filtration using a tube manifold to minimise backwash |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111832A (en) * | 1975-11-22 | 1978-09-05 | Bayer Aktiengesellschaft | Process for regenerating spent vanadium oxide containing oxidation catalysts |
| US4515899A (en) * | 1983-12-14 | 1985-05-07 | Denka Chemical Corporation | Steam regeneration of phosphorus treated vanadium-phosphorus-oxygen catalysts |
| US4596878A (en) * | 1983-12-14 | 1986-06-24 | Denka Chemical Corporation | Process for the production of maleic anhydride |
| US5521134A (en) * | 1994-02-22 | 1996-05-28 | Scientific Design Company, Inc. | Method for regenerating vanadium/phosphorus oxidation catalysts |
-
1995
- 1995-04-14 JP JP7113613A patent/JPH08332387A/en active Pending
-
1996
- 1996-04-04 AU AU53849/96A patent/AU5384996A/en not_active Abandoned
- 1996-04-04 WO PCT/US1996/004635 patent/WO1996032193A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111832A (en) * | 1975-11-22 | 1978-09-05 | Bayer Aktiengesellschaft | Process for regenerating spent vanadium oxide containing oxidation catalysts |
| US4515899A (en) * | 1983-12-14 | 1985-05-07 | Denka Chemical Corporation | Steam regeneration of phosphorus treated vanadium-phosphorus-oxygen catalysts |
| US4596878A (en) * | 1983-12-14 | 1986-06-24 | Denka Chemical Corporation | Process for the production of maleic anhydride |
| US5521134A (en) * | 1994-02-22 | 1996-05-28 | Scientific Design Company, Inc. | Method for regenerating vanadium/phosphorus oxidation catalysts |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11351523B2 (en) * | 2016-09-22 | 2022-06-07 | Johnson Matthey Davy Technologies Limited | Process for regenerating a deactivated vanadium-titanium-phosphorous catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08332387A (en) | 1996-12-17 |
| AU5384996A (en) | 1996-10-30 |
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