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WO1996033012A1 - Procede de regeneration d'un catalyseur - Google Patents

Procede de regeneration d'un catalyseur Download PDF

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Publication number
WO1996033012A1
WO1996033012A1 PCT/US1996/004718 US9604718W WO9633012A1 WO 1996033012 A1 WO1996033012 A1 WO 1996033012A1 US 9604718 W US9604718 W US 9604718W WO 9633012 A1 WO9633012 A1 WO 9633012A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
catalyst particles
reactor
recited
used catalyst
Prior art date
Application number
PCT/US1996/004718
Other languages
English (en)
Inventor
Nagato Hamashima
Masayuki Asami
Sadakatsu Suzuki
Tatsumi Ichiki
Hiroshi Ueno
Original Assignee
Abb Lummus Global Inc.
Lonza Societa Per Azioni
Tonen Chemical Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Abb Lummus Global Inc., Lonza Societa Per Azioni, Tonen Chemical Corporation filed Critical Abb Lummus Global Inc.
Priority to AU54435/96A priority Critical patent/AU5443596A/en
Publication of WO1996033012A1 publication Critical patent/WO1996033012A1/fr

Links

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
    • 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 is related to a process for treating a catalyst used in a process for the preparation of maleic anhydride by oxidizing a hydrocarbon having four carbon atoms 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, in a fluidized bed reactor.
  • 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.
  • various processes have been tried for the regeneration of the catalyst.
  • the known methods include increasing the valence of the vanadium to 3.9 to 4.6 using sulfur trioxide, by which the catalytic activity is partly regenerated (US Patent No.
  • Hei-5-329381 discloses a method where the catalyst particles used in a fluidized bed reactor are de-agglomerated or a method where the surface of the catalyst particles in a fluidized bed reactor is re-exposed, wherein a high speed gas is blown onto the catalyst particles while they are in a fluidized state in a fluidized bed reactor whereby the surface of the particles is polished due to the collision of the particles.
  • a method is disclosed where the catalyst is taken out of a fluidized bed reactor and then crushed to expose the active surface of the catalyst which is then put back into the reactor.
  • a purpose of the present invention is to provide an improved process for the efficient regeneration of a V-P-O type catalyst to improve conversion, yield and selectivity.
  • the present invention provides a process for improving the activity 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, and wherein at least a part of the catalyst particles are removed from the reactor, the less desirable catalyst particles having a flake-like configuration which have accumulated are separated and the desirable catalyst particles having the normal, generally spherical-like configuration are returned to the reactor.
  • the process may also include the step of replacing the reaction gases in the reactor with nitrogen or air before the catalyst particles are removed from the reactor or the step of replacing the reaction gas that has been removed from the reactor with the catalyst particles also with nitrogen or air prior to the separation step.
  • Fig. 1 is a graph illustrating the particle size distributions of the catalyst particles.
  • Fig. 2 shows the structure of the catalyst particles before the classification.
  • Fig. 3 shows the structure of the classified coarse powder.
  • Fig. 4, 5 and 6 all show the structure of classified fine powders.
  • 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 .
  • one such catalyst has a main crystalline component of divanadyl 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. 4,085, 1 22); 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 - 50455/1 989).
  • Separation of the flaky catalyst particles from spherical catalyst particles is carried out preferably in a dry process.
  • the dry process for the separation is carried out preferably using the force of air, more preferably using air streams in combination with centrifugal force, inertial force or gravity.
  • a classifier where classification is carried out using the action of centrifugal force and air streams.
  • Such classifiers include those generally known as turbo classifiers, microprex, multiprex zigzag classifiers, super separators, accurecut, etc. In classification using a screen, it is difficult to separate the flaky catalyst efficiently and selectively.
  • fine particulate, spherical catalyst may be simultaneously separated and removed together with the flaky catalyst.
  • the separation equipment is preferably operated such that most of the flaky catalyst is removed, as observed in microscopic photographs as described below. Also, the proportion of fine spherical particles removed to the flaky particles removed should be minimized. If the flaky catalyst is insufficiently removed, there is less of an increase in the activity and selectivity of the catalyst. Meanwhile, if too large a proportion of the spherical catalyst particles are removed, a large proportion of the desired catalyst is discarded, which is uneconomical.
  • the composition of the gas flow used in the separation process is not particularly limited as long as it does not cause adverse effects, such as a decrease in the activity of the catalyst.
  • a gas mixture may be used. Air is the least expensive but nitrogen, oxygen, rare gases, carbon dioxide, steam or hydrocarbons alone or as a mixture thereof can be used.
  • a gas mixture of butane and air or a reactor outlet gas may also be used.
  • the reaction gas in the reactor may be replaced with other gases such as the aforesaid gases before the catalyst is taken out of the reactor.
  • reaction gas accompanying the catalyst particles taken out of the reactor may be replaced with other gases before the separation and removal treatment is carried out.
  • the pressure in the separation treatment is not particularly limited. Operations are easier with a pressure of at least atmospheric pressure.
  • the temperature is not limited and may be room temperature. Alternatively, the treatment may be carried out at a temperature which is approximately equal to the reaction temperature so the treated catalyst is already at the reaction temperature when it is reintroduced into the reactor.
  • the step of taking the catalyst out of the fluidized bed reactor, the step of treating it for separation and the step of putting it back into the fluidized bed reactor may each be carried out continuously or batchwise.
  • a sample catalyst was a V-P-O catalyst which had been used for about two years in a reaction where n-butane was air oxidized into maleic anhydride in a fluidized bed reactor whereby its activity had decreased over time.
  • the catalyst was sampled from an outlet gas from the fluidized catalyst bed after passing through a cyclone.
  • a MELVERNSystem 3601 based on a laser light diffraction method, the particle size distributions were determined for the catalyst before the classification and for the coarse powder and the fine powder obtained from the classification. The results are as shown in Figure 1 .
  • the coarse powder obtained by the classification contained almost no particles smaller than 1 3 micron and had an average particle size somewhat larger than that before the treatment. Meanwhile, most of the fine powder obtained by the classification had a particle size of 1 to 13 microns.
  • MAH was 14 mole% and the selectivity to MAH was 63 mole %. It is seen that the conversion was very low with the fine powder, compared to the sample catalyst before the classification, even though the average particle size of the fine powder was smaller. In the reaction for forming MAH, there is a general tendency that the selectivity is higher as the conversion is lower. However, in this Comparison, the selectivity was low, compared to that with the catalyst before the treatment even though the conversion was lower.
  • MAH was 28 mole % and the selectivity to MAH was 71 mole %. That is, the conversion was improved, compared to the result with the catalyst before the classification shown in Comparison 1 . Moreover, it is seen that the selectivity to MAH was also improved, even though the conversion was high compared to that with the catalyst before the classification. Compared to the results in Comparison 2 for the fine powder, the conversion and the selectivity in the present invention are much higher and the yield of MAH was doubled.
  • a V-P-O catalyst which had been used for about two years in a reaction where n-butane was air oxidized to prepare maleic anhydride in a fluidized bed reactor whereby its activity had decreased was sampled from a sampling opening located approximately at the center of the catalyst bed.
  • One hundred grams of this catalyst were classified using the same apparatus as in Example 1 at room temperature, a rotor rotation of 3500 rpm, air in the amount of 2.0 m 3 /min. and a channel air pressure of 2.0 kgf/cm 2 . There was obtained 99 g of coarse powder and 1 g of fine powder.
  • FIG 5 A scanning electron microscopic photograph of the fine powder obtained is shown in Figure 5.
  • a large amount of flaky particles as well as fine particles were observed in the fine powder obtained by the classification, similar to Figure 4.
  • the photograph in Figure 6 is of a lower magnification than that in Figure 5. It can be seen that the amount of particles with spherical shape is very small. Therefore, in the sample catalyst used in this Example, the flaky particles were selectively separated in the fine powder in the classification using the air classifier.

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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)
  • Furan Compounds (AREA)
  • Combined Means For Separation Of Solids (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

La présente invention se rapporte à l'amélioration d'une activité d'un catalyseur utilisé dans un procédé de préparation d'un anhydre de l'acide maléique par oxydation de n-butane dans un réacteur à lit fluidisé, dans lequel le catalyseur comporte des oxydes de composés de vanadium-phosphore. Les particules du catalyseur sont sorties du réacteur et le catalyseur en flocons présent avec les particules du catalyseur est séparé et enlevé.
PCT/US1996/004718 1995-04-17 1996-04-05 Procede de regeneration d'un catalyseur WO1996033012A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54435/96A AU5443596A (en) 1995-04-17 1996-04-05 Process for the regeneration of a catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7/114033 1995-04-17
JP7114033A JPH08281126A (ja) 1995-04-17 1995-04-17 使用された触媒の処理方法

Publications (1)

Publication Number Publication Date
WO1996033012A1 true WO1996033012A1 (fr) 1996-10-24

Family

ID=14627357

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/004718 WO1996033012A1 (fr) 1995-04-17 1996-04-05 Procede de regeneration d'un catalyseur

Country Status (3)

Country Link
JP (1) JPH08281126A (fr)
AU (1) AU5443596A (fr)
WO (1) WO1996033012A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7195783B2 (en) 1999-07-09 2007-03-27 Fx Life Sciences International Gmbh Hypericin and hypericum extract: specific T-type calcium channel blocker, and their use as T-type calcium channel targeted therapeutics

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688401A (en) * 1949-09-29 1954-09-07 Standard Oil Co Flotation of active catalyst from spent catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688401A (en) * 1949-09-29 1954-09-07 Standard Oil Co Flotation of active catalyst from spent catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7195783B2 (en) 1999-07-09 2007-03-27 Fx Life Sciences International Gmbh Hypericin and hypericum extract: specific T-type calcium channel blocker, and their use as T-type calcium channel targeted therapeutics

Also Published As

Publication number Publication date
AU5443596A (en) 1996-11-07
JPH08281126A (ja) 1996-10-29

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