WO2013064956A1 - Procédé de recyclage de catalyseurs de styrène usagés - Google Patents

Procédé de recyclage de catalyseurs de styrène usagés Download PDF

Info

Publication number
WO2013064956A1
WO2013064956A1 PCT/IB2012/055962 IB2012055962W WO2013064956A1 WO 2013064956 A1 WO2013064956 A1 WO 2013064956A1 IB 2012055962 W IB2012055962 W IB 2012055962W WO 2013064956 A1 WO2013064956 A1 WO 2013064956A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
process according
styrenic
styrene
weight
Prior art date
Application number
PCT/IB2012/055962
Other languages
German (de)
English (en)
Inventor
Florina Corina Patcas
Yong Liu
Martin Dieterle
Original Assignee
Basf Se
Basf (China) Company Limited
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 Basf Se, Basf (China) Company Limited filed Critical Basf Se
Publication of WO2013064956A1 publication Critical patent/WO2013064956A1/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
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • 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
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/881—Molybdenum and iron
    • 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 invention relates to a process for the preparation of a novel styrene catalyst from a used styrene catalyst.
  • iron oxide-containing catalysts such as those used for the dehydrogenation of hydrocarbons, for example for the dehydrogenation of isopentene to isopentadiene (isoprene) or of ethylbenzene to styrene into consideration. These generally have a ceria content in the range from 1 to 25% by weight, in particular from 5 to 15% by weight.
  • Such catalysts are described, for example, in EP 1 027 028 A1, DE 101 54 718 A1 and EP 0 894 528 B1.
  • the catalysts usually also contain compounds of numerous other elements such as iron, potassium, molybdenum, magnesium, calcium, tungsten, titanium, copper, chromium, cobalt, nickel, vanadium and others.
  • styrene catalysts consist mainly of oxides of the elements iron and potassium, wherein the iron is predominantly present as a trivalent oxide.
  • styrenic catalysts include various elements such as cerium, molybdenum, tungsten, vanadium, calcium, magnesium, etc. in oxidic form as promoters.
  • the cerium is present as ceria CeO 2 in substantial amounts of about 1 to 25% by weight in the styrene catalyst.
  • the trivalent iron (Fe (III)) is partially reduced to divalent iron (Fe (II)). This produces magnetite FesC.
  • styrene catalysts gradually lose their activity.
  • several processes such as potassium loss by evaporation, the irreversible formation and deposition of coke or the increasing reduction of trivalent iron to divalent iron.
  • the deactivated styrene catalysts are removed from the reactors and replaced by new catalysts.
  • large quantities of used styrene expansion catalysts are produced annually worldwide, and their reprocessing is economically very interesting due to the ever-increasing prices for the doping components.
  • the expansion catalyst is optionally ground, calcined, possibly mixed with fresh raw materials (iron oxides, potassium compounds, promoters), extruded into moldings and calcined again.
  • the expansion catalyst contained therein is subjected to one to two additional calcining, usually at quite high temperatures of up to 1000 ° C. As a con- sequence, the specific surface area of the catalyst decreases in comparison with a catalyst made exclusively from fresh raw materials.
  • styrene catalysts prepared in the described way from expansion catalysts therefore often have the disadvantage that their activity is lower compared to catalysts which have been prepared exclusively from fresh raw materials.
  • WO 2007/009927 A1 describes a process for the preparation of dehydrogenation catalysts using secondary raw material which is obtained by working up used catalysts. In this method, no chemical separation of the catalyst components in compounds of the individual metals. Rather, 10 to 70 wt .-% of a calcined and ground used, iron oxide-containing catalyst with 30 to 90 wt .-% of a fresh iron oxide-containing catalyst material is mixed.
  • KR2002-0093455 describes a process for recovering ceria from spent dehydrogenation catalysts used to produce styrene from ethylbenzene.
  • the used catalyst is ground wet, for example in a ball mill to a particle size of 0.1 to 5 ⁇ . After filtering off the milled catalyst and adding acid to the solid, a mash is prepared with a pH of 0.5 to 3.0, which is filtered once more.
  • the solid residue is mixed with water and dispersed with the addition of organic dispersants using ultrasound, whereupon two phases are formed, wherein the lower phase is to contain iron oxide (magnetite) and the upper phase ceria.
  • the very fine grinding of the used catalyst is expensive, the organic dispersants used can pollute the wastewater.
  • An object of the present invention is to provide a process for producing a novel styrene catalyst from a used styrenic catalyst, wherein the specific surface area of the new styrenic catalyst is at least equal to that of the used catalyst.
  • This object is achieved by a process for the reprocessing of used styrene catalysts, in which a used catalyst is completely dissolved and its components are isolated from the solution as a solid and used to prepare a new styrene catalyst.
  • the invention thus provides a process for the preparation of a novel styrene catalyst from a used styrene catalyst, comprising the steps
  • step (iv) shaping and calcination of the solid mixture obtained in step (iii).
  • cerium-containing catalysts which are reprocessed by the process according to the invention contain compounds of at least the following metals:
  • Cerium corresponding to 1 to 25 wt .-% CeÜ2, in particular 5 to 15 wt .-% CeÜ2.
  • the catalysts additionally contain compounds of
  • Molybdenum corresponding to 0.1 to 10 wt .-% M0O3, and / or
  • Magnesium corresponding to 0 to 10 wt .-% MgO.
  • the catalysts in small amounts may contain other elements that are included as typical impurities in the primary iron oxides used.
  • the catalysts contain oxides of iron, potassium, and cerium. In a further embodiment, the catalysts contain oxides of iron, potassium, molybdenum, cerium and calcium. In a further embodiment, the catalysts contain oxides of iron, potassium, molybdenum, cerium, calcium and magnesium.
  • the styrene catalyst Before treating the used styrene catalyst with an aqueous acid in the first step (i) of the process of the invention, the styrene catalyst may be heated (calcined) in an oxygen-containing atmosphere to oxidatively remove any coke and organic residue present.
  • oxygen-containing gas is preferably used air, it can also be used lean air.
  • This calcining step may take place at temperatures between 400 ° C and 1100 ° C, preferably between 500 and 1000 ° C, more preferably between 600 and 900 ° C.
  • the catalyst can be calcined stationarily on sheets in a muffle furnace or in a rotary kiln or in the fluidized bed.
  • calcination will also oxidize the magnetite in the catalyst to hematite, i. All Fe (II) cations are converted to Fe (III) cations. Furthermore, any existing Ce (III) compounds are converted into CeO 2.
  • the spent styrene catalyst may be washed with water at pH values of 7 to 12 before treatment with an aqueous acid in the first step (i) of the process according to the invention.
  • the potassium compounds are removed from the catalyst, which later saves the acid for the neutralization of the potassium and the typical variation of the potassium content and the amount of bound anions (such as chloride, sulfate, nitrate) are reduced in the used catalyst.
  • the used catalyst prior to treatment with an aqueous acid, may be mechanically comminuted, such as by grinding or crushing. A smaller particle size is favorable for the subsequent dissolution stage. Of course, the mechanical comminution of the catalyst can also be done after heating.
  • the used catalyst is comminuted such that the mean particle diameter is in the range from 1 to 700 ⁇ m, preferably from 5 to 500 ⁇ m, in particular from 10 to 200 ⁇ m.
  • the order of steps of crushing, washing and heating is arbitrary.
  • the used catalyst is first crushed, then washed and finally heated.
  • the used styrene catalyst is treated with an aqueous acid, for example an inorganic (eg hydrochloric, sulfuric, nitric acid) or organic acid (eg acetic acid, formic acid, ascorbic acid, citric acid, etc.). or a mixture of two or more acids, treated at pH ⁇ 0.5.
  • an aqueous acid for example an inorganic (eg hydrochloric, sulfuric, nitric acid) or organic acid (eg acetic acid, formic acid, ascorbic acid, citric acid, etc.). or a mixture of two or more acids, treated at pH ⁇ 0.5.
  • the metal oxides contained in the catalyst are at least partially converted into salts and go into solution. Whether the catalyst is completely or partially dissolved can be determined by the ratio of acid to catalyst (stoichiometric / substoichiometric) and over the reaction time.
  • a slightly more than stoichiometric amount (10 to 20% acid excess) is used and the reaction is carried out until the entire solid is dissolved. If only a partial dissolution is intended, a substoichiometric or just stoichiometric amount (0 to 50% acid deficiency) is used and the reaction time is kept sufficiently short.
  • the partial dissolution of the used catalyst, especially the iron oxide, may be sufficient to increase the specific surface area of the catalyst without consuming an unnecessary amount of chemicals.
  • a used styrenic catalyst will contain sufficient iron (II) compounds to reduce the insoluble ceria CeO 2 present to soluble cerium (III) compounds.
  • a reducing agent such as hydrogen peroxide, formic acid, oxalic acid, hydrazine or other technically customary reducing agent may be required to completely convert the ceria into the soluble Ce (III) salt of the respective acid.
  • the concentration of the aqueous acid may be, for example, from 5 to 99.9% by weight, preferably from 10 to 80% by weight, particularly preferably from 25 to 75% by weight.
  • the pH of the aqueous acid is from -2 to 0.5, preferably from -1, 5 to 0.4, more preferably from -1, 1 to 0.
  • the pH of the acidic solution may increase with increasing dissolution of constituents increase the used catalyst.
  • the stoichiometric ratio of acid to catalyst may be from 10 to 200%, preferably between 20 and 150%, more preferably between 50 and 120%.
  • the stoichiometric ratio is understood to be the theoretical ratio of acid to the metal ions to be dissolved in the catalyst, which is necessary for the formation of stable metal salts at the treatment temperature.
  • the acid solution may be heated at reflux at a temperature of 10 ° C up to 120 ° C. Preference is given to a temperature between 20 ° C and 80 ° C, more preferably between 20 ° C and 60 ° C.
  • the dissolution process is carried out in a period between 0.5 h and 24 h. This process step produces an aqueous solution or a suspension in which some or all of the metal cations from the used catalyst are in the form of dissolved salts.
  • the carbonates possibly contained in the used catalyst produce carbon dioxide.
  • the dissolution in several ways. For example, you can submit the expansion catalyst in demineralised (DI) water and gradually add concentrated acid until the desired acid: catalyst ratio is achieved. Alternatively, you can submit the full amount of acid in deionized water and add the catalyst in portions.
  • DI demineralised
  • the weight ratio between the expanded catalyst solid and the amount of acidic liquid is maintained between 1: 1 and 1:20 to allow for good dispersion and thorough mixing of the solid. Preference is given to a ratio between 1: 2 and 1:15, more preferably between 1: 5 and 1:10.
  • the solution or suspension obtained by the acid treatment of the expansion catalyst is converted into a solid, for. B. by spray drying or precipitation and optionally oxidizing calcination.
  • the previously dissolved metal cations are present in this solid as oxides, oxide hydroxides, hydroxides or carbonates.
  • the acid solution or suspension is prepared by adding a hydroxide, carbonate or bicarbonate of an alkali metal (eg Li, Na, K) or alkaline earth metal (eg Ca, Mg) or of ammonia up to one pH value from 5 to 12 like.
  • a final pH is adjusted between 7 and 10.
  • the precipitate is separated from the liquid phase (filtration, centrifugation) and washed several times with deionised water.
  • the acid is removed from the acidic solution or suspension. For example, it is possible to evaporate the water or to spray-dry the solution.
  • the resulting solid can be washed one or more times with demineralized water to any inorganic anions such.
  • the solid As chloride, sulfate or nitrate to remove. Thereafter, the solid can be calcined at a temperature of 300 ° C to 1000 ° C in air.
  • the metal hydroxides or other metal salts contained are decomposed and / or oxidized and the respective metal oxides are formed.
  • the solid obtained in the second step (ii) of the process of the invention may serve as a precursor to a novel styrenic catalyst.
  • a novel styrenic catalyst for this purpose, in the third step (iii) of the method according to the invention after analysis, if necessary, missing components and promoters such.
  • missing components and promoters such as potassium in the form of oxides, hydroxides, carbonates or other compounds can be added to obtain the desired catalyst composition.
  • the novel catalyst comprises compounds of the following elements (contents based on the elemental oxides): iron - 50 to 90 wt .-%, potassium - 1 to 30 wt .-%, cerium - 1 to 20 wt .-% , Molybdenum - 0 to 10 wt .-%, tungsten - 0 to 10 wt .-%, vanadium - 0 to 10 wt .-%, magnesium - 0 to 10 wt .-%, calcium - 0 to 10 wt .-% and 0 to 10 wt .-% oxides of other metals such as Cr, Co, Ni, Cu, Zn, Ag, Pt, Pd, Al, La or other promoters known in the literature, wherein the contents add up to 100 wt .-% , Furthermore, auxiliaries may be added to the catalyst precursor in order to improve the processability, the mechanical strength and the pore morph
  • the solid mixture obtained in step (iii) is processed to form a new catalyst by conventional methods of shaping (kneading, extruding, drying) and calcining.
  • the solid mixture can be tabletted, sphered in a granulating drum or mixed with water or an aqueous solution of sugar, starch, polyvinyl alcohol, polyvinylpyrrolidone or the like in a blender or kneader and then extruded into various forms.
  • molded articles are cylinders, rings, star bodies and honeycomb bodies.
  • the optionally moist moldings are dried at temperatures of 50.degree. C. to 500.degree. Preferably, temperatures of 80 to 350 ° C are used.
  • the drying can z. B. held in drying trays on sheets, in drying drum or on belt driers.
  • the subsequent calcining of the catalyst is preferably carried out in a rotary kiln at temperatures between 500 ° C. and 1100 ° C., preferably between 700 and 1000 ° C.
  • the novel catalyst obtained by the process according to the invention has a greater specific surface area according to the invention than the old expansion catalyst. As a rule, its activity is also increased compared to the expansion catalyst.
  • Another object of the invention is a styrene catalyst, obtainable by one of the methods described above.
  • the new catalyst obtained from recycled expansion catalyst is used in the dehydrogenation of ethylbenzene to styrene with steam as well as a catalyst prepared from only new raw materials.
  • the expansion catalyst from a styrene reactor had a composition (in wt .-% as metals) Fe: 48.0; K: 8.0; Ce: 7.2; Mg: 1, 1; Ca: 1, 5; Residual content of other promoters, oxygen and carbon.
  • the specific surface area was 2.7 m 2 / g.
  • the phase composition of the expansion catalyst determined by XRD analysis (Cu K-alpha cathode), shows the following Crystallographic Phases: Magnetite FesC, Cerianite CeÜ2, Potassium Molybdate K2M0O4, Potassium Carbonate Hydrate K 2 C0 3 x 1, 5 H 2 0, Kalicinite KHCO3.
  • the solid then still contained 0.12 wt .-% Cl and 8.0 wt .-% Ce, 3.7 wt .-% K, 1, 3 wt .-% Mg, 1, 4 wt .-% Mo, 1, 5 wt .-% Ca and had a specific surface area of 1.2 m 2 / g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un nouveau catalyseur de styrène à partir d'un catalyseur de styrène usagé.
PCT/IB2012/055962 2011-10-31 2012-10-29 Procédé de recyclage de catalyseurs de styrène usagés WO2013064956A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11187216.4 2011-10-31
EP11187216 2011-10-31

Publications (1)

Publication Number Publication Date
WO2013064956A1 true WO2013064956A1 (fr) 2013-05-10

Family

ID=48191451

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2012/055962 WO2013064956A1 (fr) 2011-10-31 2012-10-29 Procédé de recyclage de catalyseurs de styrène usagés

Country Status (1)

Country Link
WO (1) WO2013064956A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691262A (en) * 1994-10-18 1997-11-25 Basf Aktiengesellschaft Regeneration of catalysts used in oxidative dehydrogenation of alkylaromatics and paraffins
CN101623643A (zh) * 2008-07-08 2010-01-13 中国石油化工股份有限公司 失活乙苯脱氢制苯乙烯催化剂的再生方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691262A (en) * 1994-10-18 1997-11-25 Basf Aktiengesellschaft Regeneration of catalysts used in oxidative dehydrogenation of alkylaromatics and paraffins
CN101623643A (zh) * 2008-07-08 2010-01-13 中国石油化工股份有限公司 失活乙苯脱氢制苯乙烯催化剂的再生方法

Similar Documents

Publication Publication Date Title
EP0849224B1 (fr) Procédé de fabrication de dioxyde de zirconium ayant une surface élevée
EP0212515B1 (fr) Utilisation d'un catalyseur pour la diminution du taux d'oxydes d'azote de gaz de combustion
EP2707123B1 (fr) Matières premières pour catalyseurs denox exempts de vanadium ou à teneur réduite en vanadium et procédé pour la préparation desdites matières premières
DE102005020630A1 (de) Herstellung von Cu/Zn/Al-Katalysatoren über den Formiatweg
DE3311681A1 (de) Verfahren zur herstellung einer oxidationskatalysator-zusammensetzung
WO1988010236A1 (fr) Procede de production de magnesie pure
DE2743812C2 (de) Verfahren zur Aufarbeitung von Buntmetallhydroxidschlamm-Abfallen
WO2015124149A1 (fr) Matière précurseur de catalyseur à base de tio2, production et utilisation
DE3042686C2 (de) Verfahren zur Herstellung eines Kupferoxid, Zinkoxid und Aluminiumoxid sowie gegebenenfalls Boroxid enthaltenden Katalysators
EP1379470B2 (fr) Oxydes de fer presentant un degre eleve d'affinage
EP0092108B1 (fr) Procédé pour le traitement d'eau usée acide contenant des composés d'aluminium et de fer
EP0804962B1 (fr) Procédé de préparation de poudres d'oxydes mixtes de catalyseurs desactivés pour la concentration en oxydes d'azote dans un fluide
DE3390076T1 (de) Verfahren zur Herstellung von wasserfreiem Aluminiumchlorid
DE2012902C3 (fr)
DE4303715A1 (de) Chromfreier Katalysator auf Basis Eisenoxid zur Konvertierung von Kohlenmonoxid
DE2813370A1 (de) Verfahren und vorrichtung zur gewinnung von salpetersaeure aus nitraten
DE2905203A1 (de) Verfahren zur behandlung von bauxit o.ae. rohmaterial
DE60221443T2 (de) Mit hochreinem eisenvorläufer hergestellter fischer-tropsch-katalysator und herstellungsverfahren
WO2013064956A1 (fr) Procédé de recyclage de catalyseurs de styrène usagés
US20130109560A1 (en) Process for reprocessing spent catalysts
US20130109898A1 (en) Process for reprocessing spent styrene catalysts
WO2013064965A1 (fr) Procédé de production de composés de cer (iii)
EP3541511A1 (fr) Procédé de fabrication de catalyseurs mécaniquement stables pour l'hydrogénation de composés carbonyle, ces mêmes catalyseurs et procédé d'hydrogénation
WO2013064944A1 (fr) Procédé permettant de retraiter des catalyseurs usés
EP2665680B1 (fr) Procédé de production d'éléments ou de composés d'éléments à partir de produits intermédiaires ou de produits secondaires créés lors de la production de dioxyde de titane

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12844744

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12844744

Country of ref document: EP

Kind code of ref document: A1