EP2720791A1 - Catalyseur oxyde mixte contenant du cobalt et du molybdène, ainsi que sa production et son utilisation comme catalyseur de conversion du gaz à l'eau - Google Patents

Catalyseur oxyde mixte contenant du cobalt et du molybdène, ainsi que sa production et son utilisation comme catalyseur de conversion du gaz à l'eau

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Publication number
EP2720791A1
EP2720791A1 EP12728216.8A EP12728216A EP2720791A1 EP 2720791 A1 EP2720791 A1 EP 2720791A1 EP 12728216 A EP12728216 A EP 12728216A EP 2720791 A1 EP2720791 A1 EP 2720791A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
mixed oxide
filter cake
oxide catalyst
molybdenum
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12728216.8A
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German (de)
English (en)
Inventor
Juliane Meese-Marktscheffel
Armin Olbrich
Matthias Jahn
Stefan Vodegel
Christoph IMMISCH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HC Starck GmbH
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HC Starck GmbH
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Filing date
Publication date
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Publication of EP2720791A1 publication Critical patent/EP2720791A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J35/613—
    • B01J35/615—
    • 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
    • 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
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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 mixed oxide catalyst, process for its preparation and its use, in particular for use as a shift catalyst in the
  • Mg titanates may act as support materials while the sulfides of cobalt and molybdenum are the effective catalytic centers.
  • catalysts are prepared by impregnation of support materials of Al oxides, Al-Mg spinels or similar compounds with soluble salts of the active metals (catalytically active metals) and subsequent thermal decomposition of these salts.
  • the subsequent activation by sulfidization is usually carried out with H 2 S or H 2 S-containing gas mixtures.
  • the required high surface area is already present in the carrier material in the catalysts according to the prior art, which are available in various forms (spheres, cylinders,
  • the catalyst is used according to the prior art as granules, extrudate or pellet in a fixed bed of bed, wherein the catalyst usually has a BET specific surface area of from 70 to 130 m 2 / g.
  • Known catalysts consist mostly of Al 2 0 3 as a carrier material. Studies were carried out in which Al 2 0 3 was gradually replaced by Ti0 2 or containing Al 2 0 3 -containing support material to 23 wt.% MgO. Furthermore, MgAl 2 0 4 is also used as support material. MoO 3 (molybdenum oxide) is used in proportions of 8 to 17.5 wt%, CoO 2.0 to 5.0%.
  • Catalyst with a gas mixture of hydrogen and hydrogen sulfide is obtained.
  • the alumina used had a specific surface area of 350 m 2 / g.
  • Laniecki et. al., Applied Catalysis A: General 196 (2000), pp 293-303 describe Ni-Mo sulfides as catalytically active components on Al 2 0 3 , Ti0 2 and Zr0 2 as
  • Molybdenum is applied to the support material by impregnation with ammonium heptamolybdate and nickel by impregnation of nickel nitrate. Subsequently, calcination and again activation with H 2 S / H2 gas mixtures.
  • the patent US006019954 A discloses a catalyst with Co, Ni, Mo and / or W as active components on Ti0 2 as a support material, which may also contain MgO and / or Al 2 0 3 as further carrier oxides. According to Example 1, a solution of
  • compositions which also contain TiO 2 as
  • US 4452854 describes a catalyst which catalyzes the conversion of carbon monoxide according to the water gas shift reaction in sulfur-containing, so-called acid gases.
  • the catalyst contains known sulfur-active metal oxides or metal sulfides on shaped bodies of support material.
  • the basic composition of the catalyst are oxides or sulfides of cobalt and molybdenum on alumina as support material.
  • the catalytic properties of these known supported catalysts are improved according to the disclosure of US4452854 by the simultaneous addition of alkali metal compounds and manganese oxides or manganese sulfides.
  • US 4021366 describes a continuous process for the production of
  • the high-temperature shift is performed in a temperature range of 360 to 530 ° C.
  • the catalysts used are iron oxide catalysts, some doped with chromium or aluminum.
  • the iron oxide catalysts are insensitive to small amounts of sulfur.
  • the sulfur load and the temperature should be as constant as possible, since the catalyst activity is greatly reduced by the alternating sulfidation and desulfidation under fluctuating conditions.
  • the low-temperature shift takes place at temperatures of 210 to 270 ° C. It come
  • Copper catalysts are used. However, copper absorbs almost all of the sulfur and chlorine contained in the gas and is thereby deactivated. in the
  • High temperature range are specific volume flows from 1000 to 3000
  • V n 1000-3000 m 3 /) (h ⁇ m 3 catalyst)) and in the low temperature range of 2000 to 5000 standard cubic meters per hour per m 3 of catalyst.
  • V n means standard cubic meter according to DIN 1343.
  • the carbon monoxide concentration (CO concentration) can be reduced in the combined process to up to 0.3% by volume. Further minimization of the CO concentration occurs, for example for use in
  • Fuel cells by a selective oxidation of CO to C0 2 .
  • various raw materials such as wood, straw, algae, miscanthus can be used.
  • the synthesis gas generated from these biomasses contains carbon dioxide, water and carbon monoxide depending on the origin and significant amounts of different impurities, such.
  • the object of the present invention is therefore to improve the state of the art and to provide a catalyst which does not have the disadvantages described above.
  • the object of the present invention was in addition to the fundamental catalytic activity for the water gas shift reaction (H 2 / CO ratio at least 1.75 mol / mol), the insensitivity of the catalyst to be developed over the
  • Another object of the invention was to provide a catalyst whose
  • Particles are such that in the catalyst bed in the reactor as low as possible pressure loss.
  • a mixed oxide catalyst also called catalyst
  • a support material selected from the group of alumina, magnesium oxide and titanium oxide and / or mixtures thereof, and cobalt oxide and / or molybdenum oxide as active catalyst components, wherein the active catalyst components in Support material are distributed nanodisperse, dissolved.
  • the catalyst active components serve to adjust the water gas equilibrium, ie they cause an increase in the H 2 : CO ratio in the gas outlet to the gas inlet in the reactor containing the catalyst. Due to this shift of the H 2 : CO ratio to higher values, as close as possible to the thermodynamic
  • the catalyst active components are distributed nanodispersed in the support material.
  • the longest diameters of the individual metal oxide components are less than or equal to ⁇ 100 nm, preferably ⁇ 50 nm, more preferably ⁇ 10 nm.
  • the distribution of the active metal components in the support material can be atomic, ie the active metal components form common crystal lattices with the carrier material.
  • phase MgO and Al 2 0 3 in addition to the phases MgO and Al 2 0 3, the phases such as MgAI 2 0 4 , CoAI 2 0 4 , CoMo0 4 and MgMo0 4 are present in the catalyst.
  • a uniform distribution of the active components in the carrier matrix can be seen from the EDX measurements on sections or fracture surfaces of the catalyst, FIG. 6.
  • FIG. 1 schematically shows the uniform distribution of cobalt oxide and molybdenum oxide on the inner surface of the pore-coated carrier material and in the carrier material itself by circles and crosses.
  • the catalysts of the prior art which typically by impregnation of moldings of support material with solutions of the active metals and subsequent
  • the catalysts of the present invention enable almost complete adjustment of the thermodynamic water gas balance.
  • the volume ratios of H 2 : CO of greater than or equal to> 2 and at 350 ° C. of> 4 are achieved.
  • the catalyst according to the invention is characterized in particular by the fact that it can be used for the acid gas shift reaction, ie that the crude gas from the biomass gasification can be fed directly to the catalyst without prior extensive purification. This means that the most diverse biomasses, which naturally also have different impurities, can be used. Without this possibility, an economic extraction of, for example, synthetic diesel from the gasification of biomass could not be realized.
  • the catalyst of the present invention may contain 1 to 30 wt% of active metal component.
  • the catalyst contains 5 to 25 wt .-%, particularly preferably 15 to 25 wt .-% active metal component.
  • the content of active metal components may also be less than 1% by weight, or 0.1 to 1% by weight.
  • the catalyst according to the invention contains 0.1 to 10 wt.% Sulfate, wherein the sulfate ions substitute the oxide ions of the crystal lattice in the catalyst.
  • the catalysts according to the invention preferably contain from 1 to 10% by weight, from 2 to 8% by weight of sulfate, more preferably from 2 to 6% by weight of sulfate, particularly preferably from 1 to 5% by weight, of sulfate. In a further embodiment, the catalyst may contain from 0.1 to 1% by weight of sulfate.
  • the sulfate ions can positively influence the activation of the catalyst.
  • self-activation without the addition of H 2 S is possible in the case of the catalysts according to the present invention.
  • the sulfate ions positively affect the catalytic activity and the
  • the catalyst according to the invention has a BET specific surface area, measured according to ASTM D 3663, of 30 to 250 m 2 / g, preferably 50 to 210 m 2 / g.
  • Particularly preferred catalysts have a specific
  • the invention also provides a process for the preparation of the mixed oxide catalyst.
  • the process for the preparation of mixed oxide catalyst according to the present invention comprises the following steps: a) reaction of a solution comprising a precursor for at least one catalyst active component and at least one support material by simultaneous or
  • step b) drying the filter cake from step b) at temperatures of 50 ° C to 200 ° C and generation of an intermediate product
  • step d) suspending the intermediate of step c) into a slurry, wherein the slurry is mixed with the addition of base at temperatures in the range between
  • the mixed oxide catalyst can be prepared by a process which comprises the following steps: a) reaction of a solution containing the precursor for at least one catalyst active component, at least one support material by simultaneous or sequential addition of bases and molybdenum-containing solution into a basic salt
  • step b) drying the filter cake from step b) at temperatures of 50 ° C to 200 ° C and generation of an intermediate product
  • step d) suspending the intermediate from step c) to a slurry, wherein the slurry is stirred with the addition of base at temperatures ranging between room temperature and 102 ° C, within 10 minutes to 2 hours, and
  • step d filtration of the intermediate product from step d), production of a second filter cake and displacement of the second filter cake, optionally with an organic binder;
  • At least one compound from the group consisting of cobalt sulfate, sodium molybdate, ammonium dimolybdate and nickel sulfate can be used as the precursor for the catalyst active component.
  • FIG. 3 shows the simplified process scheme for the preparation of the catalyst according to the invention.
  • a mixed hydroxide or basic sulfate of said metals is precipitated from an aqueous metal salt solution containing aluminum sulfate and optionally magnesium sulfate and cobalt sulfate by mixing with sodium hydroxide solution and ammonia by stirring.
  • the mixing can be carried out in batch mode (batchwise) by initially introducing the metal salt solution and adding the base solution or by initially introducing the base solution and adding the metal salt solution.
  • the required quantities of metal salt solution and base solution can be simultaneously fed to a stirred mother liquor.
  • the last variant can also be advantageously extended to a continuous precipitation process by the metal salt solution and the base solution are continuously fed to the precipitation reactor and the resulting suspension is pumped out continuously or leaves the reactor through a free overflow.
  • mixed oxide catalysts are produced which have an even more homogeneous distribution of the individual components in the carrier material than the mixed oxide catalysts from a batch process.
  • Filtriers are suitable filter nipples or filter presses preferred.
  • Filtration step obtained filter cake still contains significant amounts of mother liquor and is dried together with this step in the third process.
  • drying apparatuses as shown below in the embodiment, Hordenblechtrockenair but also dryers with moving bed are.
  • the intermediate obtained from the third process step according to FIG. 3 is classified very coarsely, e.g. Plates of a few centimeters high and some
  • the drying of the intermediate product is carried out at temperatures of 70-180 ° C, preferably from 70-150 ° C, more preferably at 80-120 ° C.
  • this intermediate is not critical, as it is then in the fourth step to a fine slurry (also called Slurry) is resuspended.
  • the suspension is mixed with sodium hydroxide solution and stirred at temperatures between room temperature and 80 ° C between 10 min and 2 hours.
  • the preferred conditions for the slurry of the intermediate are the temperatures of 25-80 ° C and 10 minutes to 60 minutes stirring time. Particularly preferably, the slurry is carried out at temperatures of 25-50 ° C and a stirring time of 20-45 min.
  • the intermediate thus conditioned is then filtered again in the fifth stage of the process and this time washed with a quantity of washing water which should be sufficient to displace the mother liquor from the conditioning almost completely from the filter cake.
  • the resulting filter cake is in the sixth step of
  • starch starch, methyl cellulose, polyvinyl alcohol, and the like. and just with enough water that he can be processed into a tough, but still flowable homogeneous mass.
  • sufficiently strong mixers or kneaders are suitable as apparatuses.
  • the usually flowing freely from the mixing or kneading mass is dried again in the seventh stage of the process, where it is distributed on tray plates at a height between 1 and 5 cm and the drying is then carried out in a drying oven.
  • Hordenblechtrockenin belt dryer can be used. During this final drying, the end of the
  • the filter cake mass can be advantageously deformed by extruders or similar devices into strands, which are then dried on tray plates or belt dryers.
  • the dried precursor is calcined in the oven at temperatures between 300 ° C and 1200 ° C, preferably between 300 ° C and 1000 ° C, more preferably between 300 ° C and 800 ° C. The material must not be destroyed by movement, so the morphology of the chunks or
  • Strand sections from the drying is basically preserved and only a certain shrinkage occurs.
  • FIG. 4 shows an alternative of the method according to the invention, which relates to the addition of the molybdenum.
  • the molybdenum necessary for the catalyst can already be added in the first process step to the precipitation of the basic salts or hydroxides in the form of, for example, sodium molybdate.
  • the addition would be possible in the form of the more expensive Ammoniumdimolybdates, but it is not necessary because anyway under
  • the alternative method described in FIG. 4 makes it possible in a simpler manner to achieve an equally uniform distribution of the molybdenum in the catalyst mass.
  • the mixing time in process step 6 can even be shortened, and ammonium dimolybdate can be replaced by the less expensive sodium molybdate.
  • the molybdenum may be present in the first process step via any soluble molybdate such as molybdenum. the alkali and / or Ammoniummolybdate and the alkali and / or Ammoniumdimolybdate or alkali and / or Ammoniumheptamolybdate be introduced into the process.
  • molybdenum is introduced into the process only during the mixture in the sixth process step, preferably ammonium molybdate, ammonium dimolybdate and
  • Alkali metal oxides in the finished catalyst as no washing step follows. However, it is conceivable to subject the finished calcined catalyst to a washing, and not only to wash out the alkali metals by this washing process, but even to have an additional parameter for adjusting the specific surface area.
  • the material is better filterable and generally washable.
  • the intermediate drying crystallite size internal and external porosity and the specific surface area are influenced.
  • the intermediate drying is therefore not pure water evaporation, but it also has a formative influence on the product properties.
  • the conditioning with sodium hydroxide in the mother liquor not all sulfate in the form of sodium sulfate in the mother liquor is included, but a portion of the sulfate is incorporated into the crystal lattice of the hydroxides, so that speaks better of basic sulphates than of hydroxides.
  • the amount of incorporated sulfate depends on the one hand on the precipitation conditions in the production of the precipitate in the first
  • the conditions of the conditioning of the between dried material in the fourth step here in particular the temperature and the stoichiometric NaOH excess.
  • the sulphate content decreases with the increasing degree of titration during precipitation and increasing NaOH excess during conditioning.
  • Table 1 below shows the compositions and the sulphate contents of the mixed oxide catalysts (later also referred to as Kat) according to Examples 1 to 7 of the present invention.
  • Cat 6 has a lower sulphate content of 6% than cat 7 and is in activity, at least at lower temperatures, just below cat. 7 It can therefore be said that basic salts of mixed hydroxides with a significant sulphate content> 1% show a higher activity than the almost pure hydroxides in which only about 0.3% sulfate is contained as an impurity and thus sulfate in the inventive
  • Catalyst acts as a promoter. This property is different
  • Catalysts of the present invention of the catalysts of the prior art.
  • Another distinguishing feature is the microscopic structure of the catalyst particles. While in the catalysts according to the prior art as a rule moldings of Al 2 0 3 or MgAl 2 0 4 are used with high specific surface area as a truly pure carrier material, the surface of which is then occupied by impregnation and calcination with the active metal oxides, Figure 2 , The catalysts according to the invention essentially have a very uniform distribution of the carrier metal oxides and the
  • the catalyst according to the present invention is particularly suitable as a shift catalyst, in particular as a shift catalyst for synthesis gases from biomass gasification.
  • the thus conditioned precursor was again filtered through the filter chute and washed with 170 kg of water on the suction filter. There remained 24.9 kg filter cake.
  • This filter cake was then processed in portions in a kneader with a total of 720 g Ammoniumdimolybdat and 643 g of starch and 3 kg of water to a viscous mass. 28.9 kg of this mass were distributed on 5 Horden sheets; the dump height was about 3 cm.
  • the mixture was then dried in a drying oven at 110 ° C. in the course of 24 hours, after which the dried filter cake was split into pieces of about 4 cm by 4 cm with a spatula after about 2 hours.
  • the catalyst had the following properties:
  • Composition 78% by weight Al 2 O 3 , 1 1% by weight CoO; 9% by weight Mo0 3 , 1, 3
  • Examples 2-7 Examples 2 to 7 for the preparation of the catalysts Kat 2 to Kat 7 were carried out analogously to Example 1. However, the composition and individual process parameters were varied. The composition of the catalysts Kat 1 to Kat 7 can be found in Table 1. The following Table 2 shows the process parameters which have been varied during production for both Example 1 and Example 1
  • Examples 2 to 7 were carried out analogously to Example 1, wherein the composition of the catalyst according to Table 1 and individual process parameters, as shown in Table 2, were varied.
  • the process parameters essentially correspond to those of Example 5, except that the heating time in the oven was 6 hours instead of 8 hours.
  • Filter cake 127 kg of this filter cake were then processed in portions in a kneader with a total of 3.32 kg of ammonium dimolybdate and 1.69 kg of starch to a viscous mass. 131, 6 kg of this mass were distributed on 16 Hordenbleche; the dump height was about 3 cm. It was then in the oven at 1 10 ° C within 24
  • the catalyst had the following properties:
  • Composition 62% by weight Al 2 O 3 , 12% by weight MgO, 5% by weight CoO; 14 wt.% Mo0 3 , 7 wt.% S03
  • the catalyst was activated in a 70 l pilot shift reactor with H 2 S. It led to CO sales of up to 65%. Over time, a slight decrease in catalytic activity was too recorded.
  • the used catalyst was glossy black discolored and had only a BET of 17m 2 / g by the gases and blown dust and tar deposits.
  • the tar may condense on the catalyst and occlude the inner surface, significantly lowering catalyst activity.
  • the grain shape and size of the catalyst had been preserved over the period of use.

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Abstract

La présente invention concerne un catalyseur oxyde mixte contenant une matière support et des composants actifs de catalyseur, un procédé de production dudit catalyseur oxyde mixte, ainsi que son utilisation comme catalyseur de conversion du gaz à l'eau.
EP12728216.8A 2011-06-15 2012-06-13 Catalyseur oxyde mixte contenant du cobalt et du molybdène, ainsi que sa production et son utilisation comme catalyseur de conversion du gaz à l'eau Withdrawn EP2720791A1 (fr)

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DE102011105760A DE102011105760A1 (de) 2011-06-15 2011-06-15 Mischoxidkatalysator, sowie Verfahren zu dessen Herstellung
PCT/EP2012/061151 WO2012171933A1 (fr) 2011-06-15 2012-06-13 Catalyseur oxyde mixte contenant du cobalt et du molybdène, ainsi que sa production et son utilisation comme catalyseur de conversion du gaz à l'eau

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US9403152B2 (en) * 2013-11-25 2016-08-02 Clariant Corporation Catalyst materials useful for sour gas shift reactions and methods for using them
JP6135641B2 (ja) * 2014-11-07 2017-05-31 トヨタ自動車株式会社 膜電極接合体の製造方法
JP6128099B2 (ja) * 2014-11-07 2017-05-17 トヨタ自動車株式会社 膜電極接合体の製造方法および膜電極接合体
US10112830B2 (en) * 2014-12-08 2018-10-30 Clariant Corporation Shaped catalyst for sour gas shift reactions and methods for using them
CN104971731B (zh) * 2015-06-17 2017-07-11 福州大学 一种宽温耐硫变换催化剂及其制备方法
CN108786837B (zh) * 2017-04-26 2021-03-02 神华集团有限责任公司 耐硫变换催化剂及其制备方法
CN112090435B (zh) * 2019-06-18 2023-01-03 国家能源投资集团有限责任公司 钴钼基耐硫变换催化剂及其制备方法和应用
CN113908845B (zh) * 2021-11-04 2023-12-22 华烁科技股份有限公司 一种节能环保的制备耐硫变换催化剂的方法
CN117352756B (zh) * 2023-12-06 2024-03-01 新乡学院 一种用于锂空气电池的CeO2／CoMoO4复合材料的制备方法

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DE102011105760A1 (de) 2012-12-20
WO2012171933A1 (fr) 2012-12-20
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RU2014100966A (ru) 2015-07-20
US20140138586A1 (en) 2014-05-22
CA2838544A1 (fr) 2012-12-20

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