WO2013064965A1 - Procédé de production de composés de cer (iii) - Google Patents

Procédé de production de composés de cer (iii) Download PDF

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Publication number
WO2013064965A1
WO2013064965A1 PCT/IB2012/055989 IB2012055989W WO2013064965A1 WO 2013064965 A1 WO2013064965 A1 WO 2013064965A1 IB 2012055989 W IB2012055989 W IB 2012055989W WO 2013064965 A1 WO2013064965 A1 WO 2013064965A1
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Prior art keywords
oxide
cerium
iron
compound
iii
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German (de)
English (en)
Inventor
Nils Bottke
Markus Schubert
Markus Ruf
Christian Walsdorff
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BASF China Co Ltd
BASF SE
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BASF China Co Ltd
BASF SE
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    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
    • C07C2523/70—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

Definitions

  • the present invention relates to a process for the preparation of cerium (III) compounds, in particular of cerium (III) carbonate, starting from starting compositions comprising ceria and at least one further metal oxide.
  • the preferred starting compositions containing ceria and at least one other metal oxide are, in particular, compositions containing a relatively high proportion of cerium dioxide, so that regeneration or recovery of cerium is desirable.
  • the starting compositions containing ceria and at least one other metal oxide are dehydrogenation catalysts (for example, ethylbenzene dehydrogenation catalysts) or waste products from grinding or polishing glass containing ceria and usually silica and / or lanthana.
  • the present invention relates to a process for the preparation of a dehydration catalyst comprising iron oxide and ceria, in particular a dehydrogenation catalyst which can be used in the production of styrene (hereinafter also dehydrogenation catalysts or styrene catalysts called), starting from an above-mentioned starting composition, in particular starting from spent styrene catalyst.
  • Styrene is one of the oldest and most important raw materials for the production of plastics, e.g. Polystyrene and synthetic rubber.
  • plastics e.g. Polystyrene and synthetic rubber.
  • isothermal and adiabatic processes are known.
  • the catalysts used in ethylbenzene dehydrogenation which are used in both the adiabatic and the isothermal processes, are generally multicomposite and essentially contain iron oxide and one or more alkali metal compounds which are used in the catalyst preparation, for example as alkali metal oxides, carbonates or hydroxides. Furthermore, these catalysts typically contain various other active components (promoters), wherein as promoters, for example compounds of calcium, magnesium, cerium, molybdenum, tungsten, chromium and titanium are described in the prior art.
  • promoters for example compounds of calcium, magnesium, cerium, molybdenum, tungsten, chromium and titanium are described in the prior art.
  • Common promoters are oxides of elements of the 5th and 6th subgroup of the Periodic Table and the rare earths, for example, oxides of cerium and molybdenum (US-B 3, 904, 552) or oxides of cerium and vanadium (DE-A 28 15 812 ).
  • US-B 3, 904, 552 oxides of cerium and molybdenum
  • DE-A 28 15 812 oxides of cerium and vanadium
  • EP-A 0 181 999 describes a dehydrogenation catalyst which, in addition to iron oxide (Fe 2 O 3), potassium oxide (K 2 O) and magnesium oxide (MgO), may additionally comprise a compound of cerium, molybdenum or tungsten.
  • iron oxide component in the production of dehydrogenation catalysts various natural and synthetic iron oxides such as a-Fe 2 O 3 (hematite), v-Fe 2 O 3, iron oxide hydroxide (eg, ⁇ -FeOOH), Fe 3+ 4 (magnetite), and iron oxides are available in the art described by thermal decomposition of iron salt solutions.
  • cerium (III) oxide Ce.sub.2O.sub.3
  • cerium (III) oxalate or cerium (III) carbonate is frequently used, the cerium compound normally being used in catalyst preparation in US Pat Ceria is converted.
  • a dehydrogenation catalyst In order to prepare a dehydrogenation catalyst, the components are mixed, if appropriate with the addition of a binder, and then a catalyst form is produced from the mixture (for example by extrusion), which is then calcined at temperatures in the range from 500 to 1200.degree.
  • Coke formation in the catalytic dehydrogenation of ethylbenzene to styrene typically results in the blocking of the active sites of the dehydrogenation catalyst in the course of the production process and the gradual deactivation of the catalyst.
  • water vapor is added to the ethylbenzene.
  • Spent (i.e., deactivated) catalysts are typically removed from the reactor and sent for disposal.
  • the prior art does not describe any methods that allow consumed, i. Fully regenerate deactivated catalysts or recover valuable materials, such as cerium, from the spent catalyst.
  • aqueous grinding waste which normally contain additional small amounts of abraded silica and are usually disposed of.
  • This grinding waste can be a starting material for the recovery of cerium (III) compounds.
  • the object of the present invention is to provide a simple and inexpensive to implement process, which allows the recovery of cerium from starting compositions containing ceria and at least one other metal oxide, in particular from spent dehydrogenation catalysts and / or abrasive waste.
  • an object of the present invention was to provide a simple, inexpensive and sustainable process for the regeneration of spent dehydrogenation catalysts containing ceria and at least one further metal oxide. It has now been found that by means of the process according to the invention, ceria can be easily and quantitatively dissolved in its trivalent form in the presence of iron in the oxidation state 0 and / or I in strong acids and separated from the accompanying substances.
  • the present invention relates to a process for the preparation of cerium (II) compounds, in particular cerium (III) carbonate, comprising the steps of a) contacting a starting composition A comprising ceria and at least one further metal oxide selected from the group consisting of iron oxide (eg Fe20s), silica (S1O2), molybdenum oxide (eg M0O3), lanthanum oxide (La20s), magnesium oxide (MgO) and calcium oxide (CaO) with at least one acid S and at least one iron component E containing iron in the oxidation state 0 and / or II at a temperature in the range from 40 to 160.degree. C., preferably from 40 to 120.degree. C., particularly preferably from 60 to 160.degree. C., and a pH of less than or equal to 2, preferably in the range from -2 to 2, wherein a solution L containing cerium in the oxidation state III is obtained;
  • a starting composition A comprising ceria and at least one further metal oxide selected
  • the inventive method thus provides a simple and inexpensive process for the recovery or recovery of cerium (III) compounds, which is characterized by inexpensive starting materials, a low number of necessary process steps and ease of implementation (low equipment cost) of the individual process steps.
  • the cerium (III) compound prepared by the process according to the invention in particular cerium (III) carbonate, is distinguished by high purity and in particular a low content of nitrate ions and low admixture with other lanthanides such as praseodymium and / or neodymium.
  • the cerium (II) compound produced by means of the process according to the invention can be further converted, for example, to ceria (CeO-2), which is distinguished by a high whiteness.
  • ceria CeO-2
  • a problem with known methods for obtaining ceria is that admixtures of praseodymium and / or neodymium often lead to an adverse reddish to dark brown discoloration of the ceria.
  • the solid produced by means of the process according to the invention containing at least one cerium (III) compound, in particular cerium (III) carbonate is suitable for direct further processing into a dehydrogenation catalyst (for example styrene catalyst).
  • a dehydrogenation catalyst for example styrene catalyst.
  • starting material A used is a solid containing ceria, at least one iron oxide and at least one alkali metal oxide.
  • at least one dehydrogenation catalyst comprising ceria and at least one iron oxide which has been used and / or can be used for the catalytic dehydrogenation of ethylbenzene is used as starting composition A.
  • the starting composition A is a spent styrene catalyst which has been expanded from a plant for the catalytic dehydrogenation of ethylbenzene.
  • the starting composition A may contain:
  • 0 to 5 wt.% Preferably 0.5 to 4 wt .-%, particularly preferably 1, 5 to 2.5 wt .-% of further metal oxides.
  • the above details in% by weight relate in each case to the total amount of the starting composition A and are calculated based on the particular oxide or based on the most stable oxide under normal conditions. It is typically possible that in the starting composition A to a part mixed phases of said oxides are present.
  • the starting composition A contains at least one iron oxide selected from iron oxides normally used in dehydrogenation catalysts
  • the dehydrogenation catalysts in particular selected from the group consisting of a-Fe203 (hematite), v-Fe203, iron oxide (a-FeOOH), Fe3Ü 4 (magnetite) and synthetic iron oxides, which starting from Iron salt solutions are produced.
  • the starting composition A used is an aqueous suspension comprising ceria and silicon dioxide. More specifically, as the starting composition A, at least one waste product of grinding or polishing glass containing ceria and at least one of silica (S1O2) and optionally lanthanum oxide (La203) is used.
  • composition A may contain:
  • lanthanum compound in particular lanthanum oxide (for example La 2 O 3);
  • wt .-% 0 to 2 wt .-%, preferably 0.1 to 1 wt .-%, of at least one other compounds of metals selected from aluminum, potassium, calcium, titanium, strontium and zirconium, in particular selected from oxides of said metals.
  • the above details in% by weight relate in each case to the total amount of the starting composition A and are calculated based on the particular oxide or based on the most stable oxide under normal conditions.
  • starting composition A it is also possible to use an aqueous suspension of the abovementioned components.
  • the aqueous suspension has a density in the range of 1 to 1, 5 kg / l and / or a solids content of 5 to 30 wt .-%, in particular from 10 to 20% by weight.
  • the starting composition A may optionally be dried before step a. It is also conceivable that the starting composition A is pretreated before step a, for example by annealing, in order to separate organic impurities.
  • the at least one acid S can be selected from inorganic or organic very strong or strong acids known to those skilled in the art.
  • the at least one acid S is hydrochloric acid and / or sulfuric acid.
  • the iron component E can be added in solid form, for example as iron powder, or in the form of iron (II) salt solutions.
  • the at least one iron component E selected from the group consisting of elemental iron, iron alloy, steel (eg steel chips), steel alloy, iron (II) chloride, iron (II) carbonate, iron (II) sulfate and iron (II) - ammonium sulfate.
  • iron scrap eg iron scrap shavings
  • iron component E is used as iron component E.
  • At least one iron compound E containing iron in the oxidation stage 0 and / or II is added in order to convert the cerium (IV) present into the soluble cerium (III) form.
  • the at least one iron component E in an amount of 0.5 to 10 mol / mol, preferably from 0.5 to 2 mol / mol, particularly preferably 0.8 to 1, 2 mol / mol based on molar amount of iron used to amounts of cerium in the starting composition A.
  • the iron component E is particularly preferably used in a stoichiometric ratio, based on the molar amount of iron, to amounts of cerium in the starting composition A.
  • the at least one basic compound C is selected from the group consisting of alkali metal carbonate, alkali metal bicarbonate, alkaline earth metal carbonate, alkaline earth metal hydrogen carbonate, alkali metal hydroxide and alkaline earth metal hydroxide, preferably consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hydroxide, calcium hydroxide, especially preferably sodium carbonate and sodium hydroxide, particularly preferably sodium carbonate (eg soda Na2CC "3 -10 H 2 0).
  • the starting composition A comprising ceria and at least one further metal oxide before step a is comminuted to particle sizes with an average particle diameter (D 5 o) in the range from 50 to 500 ⁇ m, in particular from 50 to 200 ⁇ m. This can typically be done by known methods and apparatus, for example by milling.
  • the average particle diameter (D 5 o) indicates the equivalent diameter of the particles approximated as a spherical shape, with 50% (percent by volume based on the total sample) of the particles having a diameter smaller than the D 5 o value and 50% (Volume percent based on the total sample) have a value greater than the D 5 o value.
  • the mean particle diameter (D 5 o) can be determined for example by means of laser diffraction.
  • the resulting insoluble residue is typically separated and optionally washed and / or optionally dried.
  • the resulting insoluble residue is used in the further steps as starting composition A.
  • This pretreatment with at least one acid S can for example serve to wash out lanthanum oxide and / or molybdenum oxide.
  • Lanthanum dioxide and / or molybdenum oxide can be an important raw material, therefore, the said oxides can optionally be isolated from the resulting solution (aqueous phase) and recycled.
  • the starting composition A comprising ceria and at least one further metal oxide is treated before step a to separate off organic impurities. This is done in particular by annealing (burning off of organic residues) of the starting material A in an air or lean air atmosphere at temperatures in the range from 400 to 1000 ° C., preferably from 550 to 850 ° C. Typically, the solid residue obtained is used as starting composition A in the further steps.
  • Step a of the process according to the invention relates to contacting a starting composition A comprising ceria and at least one further metal oxide having at least one acid S and at least one iron component E containing iron in the oxidation stage 0 and / or II at a temperature in the range of 40 to 160 ° C and a pH of less than or equal to 2, wherein a solution L containing cerium in the oxidation state I II is obtained.
  • the contacting in step a preferably takes place at a temperature in the range from 40 to 160.degree. C., more preferably from 40 to 120.degree. C., particularly preferably from 60 to 120.degree. C., in particular from 90 to 120.degree.
  • contacting in step a is at the boiling point or near the boiling point of the mixture (containing starting composition A, iron component E and acid S).
  • the contacting in step a at the boiling point is carried out under reflux.
  • Step a of the process typically involves adding the starting composition A to at least one acid S and adding at least one iron component E, which mixture is heated to boiling. Preference is given to the temperature of the mixture (containing starting composition A, iron component E and acid S) for 10 minutes to 8 hours, preferably for 1 to 4 hours, more preferably for 0.5 to 2 hours at the corresponding temperature or held at the boiling point.
  • the contacting in step a preferably takes place at a pH value in the range from -2 to 2, preferably -1 to 1.
  • the contacting in step a) typically takes place at pressures in the range from 0.7 to 4, preferably at 0.7 to 1.2 bar, in particular at atmospheric pressure (about 1 bar).
  • step a of the process according to the invention typically a solution L containing cerium in the oxidation state III is obtained, in particular all the cerium present in the starting composition is converted into the oxidation state III.
  • a solid F1 can be obtained in step a in addition to the solution L containing cerium in the oxidation state III.
  • This solid F1 may in particular contain silica and / or molybdenum oxide.
  • the solution L obtained in step a may optionally be separated from the insoluble solid F1.
  • Step b) of the process according to the invention relates to the addition of at least one basic compound C to the solution L, a solid F containing at least one cerium (III) compound being obtained.
  • the solid F containing at least one cerium (III) compound is formed in particular by precipitation due to reduced solubilities under the given conditions. It is known to the person skilled in the art that these are always solution equilibria in connection with very sparingly soluble or practically insoluble compounds.
  • a pH in the range from 6 to 12, preferably from 7 to 9, is obtained in step b) by adding at least one basic compound C.
  • adding the at least one basic compound is carried out stepwise with adjustment of different pH stages with optional separation of the possibly obtained solid (solid phases) (fractionated precipitation).
  • the addition of a basic compound and the removal of solid obtained may be carried out in 1 to 10, preferably in 1 to 3 steps, wherein for each step, the same or different basic compounds mentioned above can be selected.
  • step b comprises the following steps: adding at least one basic compound C to the solution L to a pH
  • the temperature in step b can be lowered to temperatures in the range of 0 to 30 ° C in order to achieve as complete as possible precipitation of the cerium (III) compound (s).
  • At least one basic compound C is added to the solution L in step b at pressures in the range from 0.7 to 1.2 bar, in particular at normal pressure (about 1 bar).
  • Step c of the process according to the invention relates to the separation of the solid F containing at least one cerium (III) compound, in particular cerium (III) carbonate.
  • the solid F containing at least one cerium (III) compound may in particular contain as further constituent at least one iron compound, for example iron oxide, iron oxide hydroxide, iron hydroxide.
  • the separation of the solid F relates in particular to the separation of the solid phase (solid F) from the liquid phase (solution L).
  • the separation of the solid matter F in step c may typically be carried out by means of known separation methods and devices, for example step c may comprise a step selected from filtration, centrifugation, sedimentation, decantation and membrane filtration.
  • the separation of the solid F can be supported for example by the application of negative pressure.
  • the separation of the solid F in step c at temperatures in the range of 0 to 100 ° C, in particular from 10 to 50 ° C is performed.
  • the separation of the solid F in step c is carried out at pressures in the range from 0.7 to 1.2 bar, in particular at atmospheric pressure (about 1 bar).
  • the described process step for the separation of the solid F can also be applied correspondingly for the separation of further optionally obtained solids (for example F1, F2).
  • the solid F obtained in step c is washed and / or dried containing at least one cerium (III) compound.
  • the solid F obtained in step c is washed with a detergent, in particular water.
  • the washing of the solid F preferably takes place until a content of acid anions (such as chloride and sulfate anions) of less than 3,000 ppm, preferably less than 1,000 ppm, more preferably less than 500 ppm, most preferably less than 200 ppm (based on the dry matter of the solid F) in the solid F is reached.
  • the solid F particularly preferably contains less than 200 ppm, preferably less than 50 ppm, more preferably less than 10 ppm (based on the dry matter of the solid F) of anions.
  • ppm for the purposes of the present invention denotes mg / kg (milligrams per kilogram).
  • cerium (III) compounds relates to the use of at least one waste product from the grinding or polishing of glass as starting composition A, in particular the following steps may be encompassed: i) optionally drying the starting composition A; ii) optionally annealing (burning off organic residues) of the starting composition A in an air or lean air atmosphere at temperatures in the range of 400 to 1000
  • starting composition A preferably from 550 to 850 ° C, wherein the obtained solid residue is used in further steps as starting composition A; iii) optionally contacting the starting composition A with at least one acid S at temperatures in the range from 0 to 100 ° C, preferably from 0 to 50 ° C, preferably from 0 to 35 ° C, particularly preferably from 20 to 35 ° C, and preferably at a pH in the range of 1 to 3, in particular from 1 to 2, and separating the resulting solution, wherein the resulting insoluble residue is used in further steps as starting material A; iv) contacting the starting composition A with at least one acid S and at least one iron component E containing iron in the oxidation state 0 and / or II at a temperature in the range of 40 to 160 ° C and a pH of less than or equal to 2, preferably in the range of -2 to 2, wherein a solution L containing cerium in the oxidation state III and optionally a solid F1 becomes; v) optional separation of the solid F1
  • the present invention furthermore relates to a process for preparing a dehydrogenation catalyst comprising at least one iron oxide and at least one cerium (IV) compound comprising the preparation of a cerium (II) compound (or a solid F containing at least one cerium (III) Compound) as described above and the following steps: d) mixing the solid F containing at least one cerium (II) compound with at least one further component and optionally water, to obtain a catalyst composition K;
  • the process according to the invention for the preparation of a dehydrogenation catalyst thus provides a simple, cost-effective and sustainable process for the preparation or regeneration of dehydrogenation catalysts, in particular styrene catalysts, which is characterized by cost-effective starting materials, a low number of necessary process steps and simple implementation (low expenditure on equipment) distinguishes the individual process steps.
  • Dehydrogenation catalysts prepared by the process of the invention exhibit similarly good or improved activity, selectivity and / or stability compared to the fresh catalysts used commercially.
  • the process according to the invention for producing a dehydrogenation catalyst is characterized in particular by the fact that relatively low calcination temperatures are necessary in order to obtain stable catalysts (in particular stable to superheated steam) having good activity and selectivity.
  • Particularly advantageous properties of the dehydrogenation catalyst can be achieved if the cerium and iron compounds were at least partially precipitated together by the addition of a basic compound and thus have a particularly good (homogeneous) mixing.
  • Catalysts prepared in accordance with the invention can be used in particular for the dehydrogenation of ethylbenzene to styrene in all known processes and process variants. They are particularly suitable for use in the so-called isothermal process.
  • the dehydrogenation catalysts prepared according to the invention are typically distinguished by a low content of anions, in particular of chloride, nitrate and / or sulfate ions.
  • the dehydrogenation catalysts have a content of chloride, nitrate and / or sulfate ions of less than 3,000 ppm, preferably less than 1, 000 ppm, more preferably less than 500 ppm, most preferably less than 200 ppm to (based on the dehydrogenation catalyst or on the dry mass of dehydrogenation catalyst).
  • the process for the preparation of a dehydrogenation catalyst is directed to a process for regenerating a spent dehydrogenation catalyst, that is, a spent dehydrogenation catalyst is used as starting composition A and a solid (F) containing at least one cerium (l ll) compound and at least one iron compound is obtained, ie the cerium (III) is precipitated together with a proportion of iron.
  • the invention relates to a process for the preparation of a dehydrogenation catalyst comprising at least one iron oxide and at least one cerium (IV) compound comprising the following steps: a) contacting a starting composition A containing ceria and at least one iron oxide with at least one acid S and at least one iron component E containing iron in the oxidation state 0 and / or II at a temperature in the range of 40 to 160 ° C and a pH of less than or equal to 2, preferably in the range of -2 to 2, wherein a solution L containing cerium in the oxidation state III is obtained; b) adding at least one basic compound C, preferably at least one carbonate compound, to the solution L, wherein a solid F containing at least one cerium (III) compound and at least one iron compound (in particular iron (II) hydroxide, iron ( III) hydroxide and / or iron carbonate); c) separating and optionally washing and / or optionally drying the solid F; d) mixing the solid F with at least
  • a dehydrogenation catalyst comprising at least one iron oxide (in particular Fe 2 O 3) and at least one cerium (IV) compound (in particular ceria) is obtained.
  • Dehydrogenation catalyst comprising at least one iron oxide (in particular Fe 2+ 3) and at least one cerium (IV) compound (in particular cerium dioxide) is to be understood in the sense of the present invention as meaning that the corresponding metals can be determined in the amounts indicated in the catalyst.
  • cerium (IV) compound in particular cerium dioxide
  • the preparation of styrene catalysts typically includes:
  • the process for producing a dehydrogenation catalyst may further include pressing and / or drying the molded articles.
  • a water-containing solid F containing at least one cerium (II) compound and at least one iron compound is mixed with at least one further component, in particular with at least one further active component (dopant).
  • further active component in particular at least one compound selected from the group consisting of iron compounds (in particular oxides, eg Fe2Ü3), alkali metal compounds (in particular oxides, eg potassium oxide), alkaline earth metal compounds (especially oxides, eg magnesium oxide, calcium oxide), chromium compounds (in particular oxides, eg Cr2Ü3) and compounds (especially oxides) of elements of the 4th to 8th subgroup of the periodic table and the lanthanides are added.
  • active components it is possible to use compounds as present in the finished catalyst or compounds which convert into compounds during the production process, as are present in the finished catalyst.
  • the solids F is at least one iron oxide selected from natural and synthetic iron oxides (for example, a-Fe2Ü3 (hematite), v-Fe203, iron oxide (such as ⁇ -FeOOH), Fe3Ü 4 (magnetite), and iron oxides obtained by thermal see decomposition of iron salt solutions), potassium oxide and optionally other components, whereby a catalyst composition K is obtained.
  • natural and synthetic iron oxides for example, a-Fe2Ü3 (hematite), v-Fe203, iron oxide (such as ⁇ -FeOOH), Fe3Ü 4 (magnetite), and iron oxides obtained by thermal see decomposition of iron salt solutions
  • potassium oxide and optionally other components
  • adjuvants may also be added to improve processability, mechanical strength or pore structure.
  • auxiliaries for example binders, extrusion aids and porosity-improving agents can be used.
  • adjuvants are typically starch (e.g., potato starch), alginates, cellulose, methyl cellulose, stearic acid, graphite, and Portland cement.
  • the components are typically intimately mixed in the form of an aqueous paste directly in a mixer, kneader or preferably a Mix-Muller. They can also be slurried in a spray mixture and processed into a spray powder in a spray dryer.
  • the components are preferably intimately mixed in a Mix-Muller or kneader with the addition of water and processed into an extrudable mass.
  • the extrudable mass is then extruded, dried and calcined. The drying is typically carried out at temperatures in the range of 60 to 400 ° C.
  • Preferred strand forms include extrudates of 2 to 10 mm, preferably 2 to 6 mm in diameter.
  • the cross-section of the extrudates may be round or in other forms.
  • Particularly preferred are extrudates with rotationally symmetrical cross-section and extrudates with a star-shaped or those with a gear-toothed ("toothed-wheel") cross-section.
  • the shaping of the catalysts can also be carried out by tableting.
  • the moldings have a diameter of 2 to 10 mm, preferably from 2 to 6 mm.
  • the moldings are preferably calcined at temperatures of 500 to 1 100 ° C, in particular from 800 to 950 ° C.
  • the preparation of a dehydrogenation catalyst is described, for example, in EP 0 181 999 and EP 0 502 510.
  • the present invention relates to a composition containing at least one cerium (III) compound (solid F) obtainable by the method described above.
  • the composition according to the invention is the solid F containing at least one cerium (III) compound which can be obtained as described above.
  • the present invention relates to a composition containing at least 20 wt .-% based on the total composition of at least one cerium (III) compound, in particular cerium (III) carbonate; 0 to 80 wt .-% based on the total weight of the rare earth metal oxides of at least one iron compound and
  • compositions according to the invention contain at least one cerium (III) compound, in particular cerium (III) carbonate, typically have a loss on ignition (in particular by release of carbon dioxide and / or water) of 40 to 60% by weight. It is therefore customary to refer the content of the metal components to the annealed mass or to the total weight of the rare earth metal compounds (rare earth metal oxides) and to use in each case the masses of the respective oxides.
  • the content of anions e.g., nitrate
  • composition according to the invention comprising at least one cerium (III) compound, in particular cerium (III) carbonate, in comparison to commercially available compositions, is characterized in that it contains a small amount of nitrate (preferably less than 50 ppm, especially preferably less than 10 ppm based on the total composition).
  • compositions according to the invention can be distinguished by a small proportion of other rare earth metal compounds, in particular other lanthanoid compounds, not to mention cerium salts.
  • thanoxide (La203), praseodymium oxide (PreOn) and neodymium oxide (Nd203) may be less than 10,000 ppm, preferably less than 5,000 ppm, more preferably less than 100 ppm, based on the total weight of the rare earth metal oxides.
  • the term "rare earth metals" or "rare earth metals” includes the elements of III.
  • Subgroup of the periodic table scandium (Sc) and yttrium (Y) and lanthanum (La) and the 14 elements following the lanthanum in the periodic table.
  • the term "lanthanides” comprises lanthanum (La) and the elements on the lanthanum in the Periodic Table 14.
  • the composition described above contains from 0 to 2% by weight, preferably from 0.1 to 2% by weight the total weight of the rare earth metal oxides molybdenum oxide (eg M0O3).
  • the above-described composition contains 75 to 1000 ppm, preferably 100 to 1 000 ppm, particularly preferably 200 to 1000 ppm, based on the total weight of the rare earth metal oxides of at least one iron compound, in particular at least one iron oxide (eg Fe 2 O 3, Fe 3 O 4 ) , This is typically the case for compositions obtainable by a process described above in which, in step b, at least one basic compound C is added stepwise and with removal of iron-containing solid.
  • at least one iron oxide eg Fe 2 O 3, Fe 3 O 4
  • the composition according to the invention contains: at least 20% by weight, based on the total composition, of at least one cerium (III) compound, in particular cerium (III) carbonate; at least 50 ppm, especially at least 75 ppm, preferably at least
  • the rare earth metal oxides of at least one iron compound in particular at least one iron oxide (eg Fe 2 O 3, Fe 3 U 4 ); and 0 to 50 ppm, preferably 0 to 10 ppm based on the total composition of nitrate.
  • the above data in% by weight or ppm relate in each case to the oxides or the oxides which are stable under normal conditions.
  • the composition described above contains from 30 to 80% by weight, preferably from 30 to 70% by weight, particularly preferably from 30 to 55% by weight, based on the total weight of the rare earth metal oxides of at least one iron compound, in particular at least one iron oxide (eg Fe2Ü3, Fe3Ü 4).
  • at least one iron compound in particular at least one iron oxide (eg Fe2Ü3, Fe3Ü 4).
  • These high iron compositions are particularly useful for preparing a dehydrogenation catalyst.
  • the composition according to the invention contains at least 20% by weight, based on the total composition, of at least one cerium (III) compound, in particular cerium (III) carbonate; From 30 to 80% by weight, preferably from 30 to 70% by weight, particularly preferably from 35 to 55% by weight, based on the total weight of the rare earth metal oxides of at least one iron compound, in particular at least one iron oxide (eg Fe 2 O 3, Fe 3 O 4 ) ;
  • nitrate 0 to 50 ppm, preferably 0 to 10 ppm based on the total composition of nitrate.
  • the present invention further relates to the use of a cerium (III) compound, in particular cerium (II) carbonate, obtainable by a process as described above for producing a dehydrogenation catalyst comprising at least one iron oxide and at least one cerium (IV )-Connection.
  • a cerium (III) compound in particular cerium (II) carbonate, obtainable by a process as described above for producing a dehydrogenation catalyst comprising at least one iron oxide and at least one cerium (IV )-Connection.
  • the invention relates in particular to the use of a composition described above (or a solid containing at least one cerium (l l l) compound) for producing a dehydrogenation catalyst comprising at least one iron oxide and at least one cerium (IV) compound.
  • the present invention relates to a process for the catalytic dehydrogenation of ethylbenzene to styrene, wherein the dehydrogenation is carried out in the presence of a catalyst obtainable by a process as described above.
  • the invention relates to a process for the catalytic dehydrogenation of ethylbenzene to styrene at temperatures of 450 to 700 ° C and a pressure of 0.1 to 5 bar.
  • Example 1 Dissolution of ceria
  • ethylbenzene dehydrogenation catalyst also referred to below as styrene catalyst
  • Styrostar® ethylbenzene dehydrogenation catalyst
  • the CeC "2 content in the styrene catalyst is determined analytically by means of optical emission spectroscopy (ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry) after prior melt or microwave digestion
  • the CeC content in the styrene catalyst used is typically close to 10% by weight.
  • Example 3 In the following example, the acid insoluble residue of the styrene catalyst is quantified. For this purpose, 10 g of ground styrene catalyst (as described in Example 2) are weighed into a 600 ml beaker. After addition of 50 ml of demineralized water (demineralized water) and 100 ml of concentrated hydrochloric acid (HCl conc.) The mixture is heated on the magnetic stirrer with stirring and under reflux to boiling and stirred for a further 15 min. The insoluble residue is filtered through a black belt filter, washed and then calcined at 900 ° C.
  • demineralized water demineralized water
  • HCl conc. concentrated hydrochloric acid
  • the separated supernatant solution is analyzed by elemental analysis by emission spectrometry (ICP-OES Inductively-Coupled Plasma Optical Emission Spectrometry). It turns out that in the supernatant solution, all elements of the styrene catalyst used are present in the original proportions of the styrene catalyst used, with the exception of the cerium.
  • emission spectrometry ICP-OES Inductively-Coupled Plasma Optical Emission Spectrometry
  • the amount of the separated insoluble residue is determined gravimetrically and corresponds within the scope of the measurement inaccuracy of the cerium amount as ceria (CeCk), which is contained in the styrene catalyst used.
  • CeCk ceria
  • Example 4 Dissolution of ceria and fractionated precipitation
  • the weight gives 9.78 g of residue. A total of 51 g of saturated soda solution are consumed.
  • the proportion of cerium and iron is determined by means of optical emission spectroscopy (ICP-OES inductively-coupled plasma optical emission spectrometry).
  • the proportion of carbonate is determined gravimetrically.
  • the dried residue is mixed with concentrated sulfuric acid in a round bottom flask which is connected to at least one absorption tube.
  • the resulting carbon dioxide gas is expelled with a purified stream of air and introduced into the loaded with sodium hydroxide on carrier absorption tube.
  • the weight increase of the absorption tube and the content of carbonate are determined gravimetrically.
  • Example 5 Dissolution of styrene catalyst and fractionated precipitation
  • the weight gives 6.28 g of residue. A total of 77 g saturated soda solution is consumed.
  • the residue also contains other metals or their compounds, which are contained in the styrene catalyst used.
  • the proportion of iron is determined by atomic absorption spectrometry (AAS).
  • AAS atomic absorption spectrometry
  • cerium and the metal oxides mentioned is determined by means of optical emission spectroscopy (ICP-OES Inductive-Coupled Plasma Optical Emission Spectrometry).
  • the proportion of carbonate is determined gravimetrically as described in Example 5.
  • EXAMPLE 6 Precipitation with Addition of Sodium Hydroxide 5 g of ceria (type HSA, Rhodia) and 2 g of iron powder are weighed into a beaker and then 80 ml of demineralized water (deionised water) and 20 ml of concentrated hydrochloric acid (HCl, conc. ) was added. The mixture is heated under reflux on the magnetic stirrer until a clear, yellow solution is formed. The pH of the solution is -0.3. After the solution has cooled to room temperature, the precipitation is started by adding concentrated sodium hydroxide solution. Concentrated sodium hydroxide solution is metered in dropwise, the pH of the solution being measured continuously.
  • demineralized water deionised water
  • HCl concentrated hydrochloric acid
  • a blue-green precipitate containing iron can be observed.
  • the resulting suspension is filtered through a white belt filter and a porcelain chute.
  • Sodium hydroxide solution is added dropwise to the supernatant solution.
  • a white precipitate containing cerium precipitates At a pH of about 7 to a pH of about 8.5, a white precipitate containing cerium precipitates.
  • the resulting suspension is filtered through a white belt filter and a porcelain chute.
  • Example 7 Preparation of a Dehydrogenation Catalyst
  • the residue obtained according to Example 5 is mixed with iron oxide powder (Fe 2 C 3, hematite), calcium carbonate and water to give a CeC "2 content of about 49% by weight.
  • the mixture is placed in a Koller. After adding further dopants, the mass is rolled for about 1 h. During the mulling process, plasticizing aids are added for later extrusion.
  • the Kollermasse is then pressed via an extruder to 3 mm strands.
  • the strands thus obtained are initially predried at 300 ° C. for 3 hours and finally calcined at 900 ° C. for 1 hour.
  • the finished, red-brown strands contain just 10% Ce0 2 and about 12% K 2 0 according to elemental analysis.

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Abstract

L'invention concerne un procédé de production de composés de Cer(III) comprenant les étapes suivantes : a) mise en contact d'une composition de départ A contenant du dioxyde de cérium et au moins un autre oxyde métallique sélectionné dans le groupe comprenant l'oxyde de fer, le dioxyde de silicium, l'oxyde de molybdène, l'oxyde de lanthane, l'oxyde de magnésium et l'oxyde de calcium, avec au moins un acide S et au moins un composant fer contenant du fer au degré d'oxydation 0 et/ou II à une température dans une plage de 40 à 160 °C et à un pH inférieur ou égal à 2, une solution L contenant du Cer au degré d'oxydation III étant ainsi obtenue; b) ajout d'au moins un composé basique C à la solution L, un solide F contenant au moins un composé de Cer (III) étant ainsi obtenu; c) séparation du solide F contenant au moins un composé de Cer (III).
PCT/IB2012/055989 2011-10-31 2012-10-30 Procédé de production de composés de cer (iii) Ceased WO2013064965A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895929A (zh) * 2016-04-25 2016-08-24 广东工业大学 一种金属空气电池电极催化剂及其制备方法和应用
CN107597125A (zh) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 一种含固态钾的仲丁醇脱氢催化剂及其制备方法
CN120463490A (zh) * 2025-04-29 2025-08-12 柒星通信科技（北京）有限公司 一种用于移相器的高性能复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009101016A2 (fr) * 2008-02-12 2009-08-20 Basf Se Nanoparticules hybrides modifiées
CN101820997A (zh) * 2007-08-09 2010-09-01 巴斯夫催化剂公司 催化剂组合物
CN101955218A (zh) * 2010-05-31 2011-01-26 北京颖新泰康国际贸易有限公司 一种采用含有三价铈盐的水溶液制备四价铈化合物的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101820997A (zh) * 2007-08-09 2010-09-01 巴斯夫催化剂公司 催化剂组合物
WO2009101016A2 (fr) * 2008-02-12 2009-08-20 Basf Se Nanoparticules hybrides modifiées
CN101955218A (zh) * 2010-05-31 2011-01-26 北京颖新泰康国际贸易有限公司 一种采用含有三价铈盐的水溶液制备四价铈化合物的方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895929A (zh) * 2016-04-25 2016-08-24 广东工业大学 一种金属空气电池电极催化剂及其制备方法和应用
CN107597125A (zh) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 一种含固态钾的仲丁醇脱氢催化剂及其制备方法
CN107597125B (zh) * 2017-10-25 2020-08-28 山东齐鲁科力化工研究院有限公司 一种含固态钾的仲丁醇脱氢催化剂及其制备方法
CN120463490A (zh) * 2025-04-29 2025-08-12 柒星通信科技（北京）有限公司 一种用于移相器的高性能复合材料及其制备方法

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