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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
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
  • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
• • 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
  • B01J37/0201—Impregnation
• • 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
  • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
• • 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
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • 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
  • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
  • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
  • C01B3/0015—Organic compounds; Solutions thereof
• • 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
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
  • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
• • 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
  • C07C5/3335—Catalytic processes with metals
  • C07C5/3337—Catalytic processes with metals of the platinum group
• • 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
  • C01B2203/1064—Platinum group metal catalysts
  • C01B2203/107—Platinum 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
  • 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

Definitions

• the application relates to a catalyst for de hydrogenation as defined in claim 1 and a method for preparing the catalyst as defined in claim 9. Further, the application relates to a use of the catalyst as defined in claim 15.
• LOHCs Liquid organic hydrogen carriers
• Many LOHC com pounds are stabile at normal temperature and pressure.
• the LOHC system is promising particularly for applica tions, where safety, robustness and fast kinetics of the system are priorities.
• Catalytic dehydrogenation of some perhydrogenated LOHC candidates are mature in dustrial processes.
• DBT dibenzyl toluenes
• Reforming of cycloalkanes is based on noble metals, particulartly Pt, or on lower-cost Ni and Mo and their combinations with alkali reagents.
• Alumina is a common support in these reactions.
• Pt on carbon has been observed to be the most ac tive amongst the tested catalysts for hydrogen release from perhydrogenated dibenzyl toluenes (H18-DBT) .
• the objective is to disclose a new type cata lyst for dehydrogenation. Further, the objective is to disclose a new type method for preparing the catalyst. Further, the objective is to improve a dehydrogenation process. Further, the objective is to provide effi cient process and catalyst for releasing hydrogen in the dehydrogenation.
• a catalyst for dehydrogenation is a Pt cata lyst.
• the catalyst is prepared from a support and a Pt catalyst agent which arranged onto the support.
• Fig. 1 shows results from the tests according to three embodiments at Pt contents of 1 - 1.5 wt%.
• a catalyst for dehydrogenation is a Pt cata lyst, in which Pt catalyst agent is formed by using a Pt-precursor and is arranged on a support, and the support is selected from Ti0 2 or g-A1 2 0 3 .
• Pt catalyst agent is formed from a Pt- precursor, the catalyst agent is arranged onto a sup port which is selected from Ti0 2 or y-Al 2 0 3 in order to form the catalyst, and the catalyst is calcinated.
• the support means any sup port or carrier material, onto which any Pt catalyst agent is arranged.
• the support is in the form of powder.
• the support is selected from Ti0 2 .
• the Ti0 2 support consists of anatase-rutile system.
• the Ti0 2 support is formed from a mixture of anatase and rutile forms.
• the Ti0 2 support consists of powder.
• particles of the powder have particle size which may vary and which may be in large size range.
• particles of the powder are nanoparticles, microparticles and/or other particles.
• particles of the powder are nanoparticles and/or microparticles.
• the Ti0 2 support consists of the powder with particles which have particle size over 0.015 ym, over 0.035 ym or larger.
• the Ti0 2 support consists of the powder with nanoparticles.
• the Ti0 2 support consists of the powder with nanoparticles which have particle size 0.015 - 0.100 ym, or in an embodiment the powder with larger parti cle sizes. In a further embodiment, the Ti0 2 support consists of the powder with nanoparticles which have particle size 0.015 - 0.035 ym. In a further embodi ment, the Ti0 2 support consists of the powder with na noparticles which have particle size selected from 0.015 - 0.035 ym or over 0.035 ym. In a further embod iment, the Ti0 2 support consists of the nanopowder.
• the support is selected from y-Al 2 0 3 .
• the y-Al 2 0 3 support con sists of the powder.
• the g-A1 2 0 3 sup port has particle size of 0.02 - 32000 ym.
• Pt-content is below 2 % by weight in the catalyst.
• the Pt-precursor is select ed from H 2 PtCl 6 (chloroplatinic acid) or Pt(N0 3 ) 2 (platinium nitrate) .
• the Pt- precursor is H 2 PtCl 6 .
• the Pt- precursor is Pt(N0 3 ) 2 .
• the catalyst agent is ar ranged by an impregnation onto the support.
• the catalyst agent preferably in the form of powder or alternatively in the form which is manufactured from the powder, is arranged by an im pregnation onto the support.
• the catalyst is prepared by an incipient wetness impregna tion.
• the catalyst is prepared by an ALD-coating (atomic layer deposition coating) .
• the catalyst agent is arranged by the ALD-coating method onto the support, e.g. onto the support powder.
• the ALD- coating is carried out so that at least the support is in the powder form.
• the formed catalyst preferably in the form of powder, is arranged by means of the ALD-coating method on the substrate in order to form a catalyst system.
• any suitable ALD-coating method can be used, which is preferably suitable for the ALD-coating of the powder material. By means of the ALD-coating method an amount of noble metal needed can be reduced in the catalyst.
• the catalyst is calcinated at 450 - 540 °C. In a further embodiment, the catalyst is calcinated at 480 - 520 °C.
• the dehydrogenation catalyst is its capability to desorb hydrogen to avoid reverse reaction.
• the dehydrogena tion is a dehydrogenation of H18-DBT (perhydrogenated dibenzyl toluenes) .
• the dehydrogenation is another dehydrogenation in which hydrogen is re leased from other compounds, which are, for example, monocyclic or polycyclic alkanes.
• the product composition means any product from the dehydrogenation.
• the product composition can comprise one or more product components, e.g. hydro gen, hydrocarbons, organic liquids and/or other organ ic compounds.
• the product composition may contain also other components.
• the product compo sition mainly consists of hydrocarbons and hydrogen.
• the hydrogen can be released from the product composition.
• the product composition can be post-treated after the dehydrogena tion, e.g. after releasing hydrogen.
• the product composition can be supplied to a de sired treatment process, e.g. for energy or for refin ing the hydrocarbons or other compounds .
• the catalyst is used or uti lized in a dehydrogenation in which hydrogen is re leased, in a dehydrogenation of H18-DBT, in a dehydro genation of the compounds which are monocyclic or pol ycyclic alkanes, in use of hydrogen for different pur poses, such as for energy or for manufacturing organic gas or liquid, in a production of hydrocarbons or fuel, or in their combinations.
• cata lysts can be produced for dehydrogenation of H18-DBT. Further, the present catalysts are effective also for dehydrogenation of other substrates. The present cata lysts are capable to fast release of hydrogen. Thus, the present catalysts improve efficiency of the LOHC hydrogen release system. The present catalyst offers a possibility to release hydrogen easily and effectively. The present invention provides an industrially applicable, simple and affordable way to release hydrogen in the dehydro genation .
• This example presents a Pt catalyst with a Ti0 2 support for dehydrogenation. Further, in this ex ample, the catalyst for the dehydrogenation was proucked from the Ti0 2 support and a Pt catalyst agent.
• the Pt catalyst agent is formed from a Pt- precursor which is H 2 PtCl 6 , or alternatively Pt(N0 3 ) 2 .
• the Pt-precursor is arranged onto the support which is Ti0 2 .
• the Ti0 2 support consists of anatase-rutile sys tem which comprises a mixture of anatase and rutile forms.
• the Ti0 2 support is nanopowder which has parti cle size about 0.020 - 0.030 ym.
• the catalyst agent is arranged by an incipient wetness impregnation onto the support. In addition to the impregnated catalyst, ALD technology can be used for forming platinum layer on the titania support powder.
• the Pt catalyst is calcinated at about 500 °C, preferably for about two hours.
• This example presents a Pt catalyst with a y- A1 2 0 3 support for dehydrogenation. Further, in this ex ample, the catalyst for the dehydrogenation was proucked from the g-A1 2 0 3 support and a Pt catalyst agent.
• the Pt catalyst agent is formed from a Pt- precursor which is H 2 PtCl 6 , or alternatively Pt(N0 3 ) 2 .
• the Pt-precursor is arranged onto the support which is g-A1 2 0 3 .
• the g-A1 2 0 3 support has particle size of 25 - 40 ym.
• the catalyst agent is arranged by an incipient wetness impregnation onto the support.
• ALD technology can be used for forming platinum layer on the alumina support pow der .
• the Pt catalyst is calcinated at about 500 °C, preferably for about two hours.
• Carbon supported Pt catalyst showed the high est efficiency for the dehydrogenation of H18-DBT amongst the catalysts studied. It is known that carbon has a high surface area (200-300 m 2 /g) and typically dispersion of Pt on carbon is good, which are favora ble features for the dehydrogenation catalysts. Carbon support is also low cost and abundant, but its dura bility is weak at high temperatures in the presence of oxygen. Different hydrogen release rates were observed between two different H18-DBT batches, one at 100% and the other at 95% hydrogenation degree. For 100% hydro genated H18-DBT batch, Pt/C 1 wt% catalyst released 91 % of the theoretical maximum of hydrogen in 45 minutes.
• Metal oxides are more durable supports than carbon, and thus interesting for the dehydrogenation of H18-DBT.
• Alumina support is used in the commercial LOHC solution.
• the commercial Pt on alumina (5wt%) catalyst was not active for dehy drogenation of H18-DBT showing only 9% hydrogen re lease degree at 290 °C in 45 minutes. Instead, many in-house Pt on alumina catalysts were active towards hydrogen release from H18-DBT. However, only catalysts prepared on g-A1 2 0 3 supports were active, while that prepared on ,g-A1 2 0 3 support was not particularly ac tive.
• the titania nanopowder support is a mixture of anatase and rutile forms.
• ac tivity of Pt catalyst prepared on titania nanopowder having anatase only form was modest.
• Ti0 2 is characterised by strong metal support interaction, chemical stability, and acid-base property.
• surface area of titania is relatively low, only up to about 80 m 2 /g.
• catalysts were prepared us ing incipient wetness impregnation method.
• Catalysts were calcinated at 500 °C tempera ture. For y-Al 2 0 3 , higher calcination temperatures starting from 600 °C would lead to phase transition to low-surface area -A1 2 0 3 (completed at 1200 °C) . For titania, phase transition from anatase to low-surface area rutile starts already at about 550 °C. The calci nation temperature of 500 °C is optimum for Ti0 2 na nopowder used to increase its photocatalytic activity. Simultaneously, a small part of anatase transformed to rutile, and surface area of Ti0 2 decreased.
• Pt precursors used for the catalysts were choroplatinic acid (H 2 PtCl 6 , 38% (m/m) Pt content) and platinum nitrate (Pt(N0 3 ) 2 ).
• Pt on g-A1 2 0 3 and Ti0 2 supports were studied in comparison with commercial Pt on carbon catalyst. Be sides these catalysts, also commercial Pt/C and Pt/Al 2 0 3 were tested.
• H18-DBT substrates Two different H18-DBT substrates were used.
• Marlotherm SH Sasol was hydrogen ated in laboratory to 100% H18-DBT (hydrogenation pro cedure, SI) .
• H18-DBT with a hydrogenation degree of 95% was purchased from Hydrogenious GmbH. All the results were obtained with the latter sub strate, H18-DBT 95%.
• Formed hydrogen was collected in the measur ing glass and readings were recorded periodically. Volumetric measurement of hydrogen release rate is semi-quantitative due to the substantial effect of temperature on hydrogen density, and consequently, to hydrogen volume. Quantitative dehydrogenation degree was analysed using NMR (Varian 300 Hz, dichloro- methane-d2 solvent, filtered samples) . All hydrogen release rates were interpolated to 45 minutes for equal comparison of different catalysts.
• Fig. 1 shows some hydrogen release results from some tests with three catalysts in which Pt contents were 1 - 1.5 wt-%.
• the effi cient catalysts can be produced for dehydrogenation of H18-DBT, and also for dehydrogenation of other sub strates. Further, it was observed that the formed Pt/Ti0 2 catalyst is capable to faster release of hy drogen than the previously known alumina catalysts. Further, from Fig. 1 can be observed that the Pt- catalyst with Ti0 2 -support, which contains anatase- rutile system, has very high efficiency. Pt/Al 2 0 3 catalyst has also high efficiency, but clearly lower efficiency than the Pt-catalyst with Ti0 2 -support .
• the catalyst is suitable in different embodi ments for different kinds of dehydrogenations.
• the method for producing a catalyst for dehydrogenation is suitable in different embodiments for forming differ ent kinds of catalysts.

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• 2018
  • 2018-11-06 FI FI20185940A patent/FI128885B/sv not_active IP Right Cessation
• 2019
  • 2019-11-05 WO PCT/FI2019/050784 patent/WO2020094921A1/en active Application Filing

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