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WO2019048375A1 - Catalyseur comprenant un nouveau tamis moléculaire appartenant à la famille des eri et utilisation du catalyseur - Google Patents

Catalyseur comprenant un nouveau tamis moléculaire appartenant à la famille des eri et utilisation du catalyseur Download PDF

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Publication number
WO2019048375A1
WO2019048375A1 PCT/EP2018/073601 EP2018073601W WO2019048375A1 WO 2019048375 A1 WO2019048375 A1 WO 2019048375A1 EP 2018073601 W EP2018073601 W EP 2018073601W WO 2019048375 A1 WO2019048375 A1 WO 2019048375A1
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Prior art keywords
catalyst
molecular sieve
eri
ammonia
nitrogen oxides
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Inventor
Cristian-Renato BORUNTEA
Peter N. R. VENNESTRØM
Lars Fahl LUNDEGAARD
Avelino Corma CANÓS
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Topsoe AS
Universidad Politecnica de Valencia
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Haldor Topsoe AS
Universidad Politecnica de Valencia
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/30—Erionite or offretite type, e.g. zeolite T
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/30—Erionite or offretite type, e.g. zeolite T
    • C01B39/305—Erionite or offretite type, e.g. zeolite T using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
    • B01J29/56—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/40—Particle morphology extending in three dimensions prism-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/90—Other morphology not specified above
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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

Definitions

  • Catalyst comprising a novel molecular sieve belonging to the ERI family and use of the catalyst.
  • the present invention relates to catalyst comprising a novel molecular sieve with the ERI framework type and the use of the catalyst in catalytic reactions.
  • the invention provides a catalyst comprising a crystalline zeolite molecular sieve material belonging to the ERI framework family essentially without intergrowth of OFF zeolite, with a high Si/AI ratio and a tabular to prismatic crystal morphology.
  • Zeolite molecular sieves are classified by the International Zeolite Association (IZA) ac- cording to the rules of the lUPAC Commission on Molecular Sieve Nomenclature. Once the topology of a new framework is established, a three letter code is assigned. This code defines the atomic structure of the framework, from which a distinct X-ray diffraction patterns can be described.
  • framework type or framework topology refers to the unique atomic structure of a specific molecular sieve, named by a three letter code devised by the International Zeolite Association [Atlas of Zeolite Framework Types, 6th revised edition, 2007, Ch. Baerlocher, L.B. McCusker and D.H. Olson, ISBN: 978-0-444-53064- 6].
  • Erionite is a naturally occurring aluminosilicate zeolite [Staples, L.W. and Gard, J.A., Mineral. Mag., 32, 261 -281 (1959)] with a Si/AI ratio around 3. It is often found as an intergrowth with OFF [Schlenker, J.L., Pluth, J.J. and Smith, J.V., Acta Crystallogr., B33, 3265-3268 (1977)].
  • ERI Erionite
  • US Patent 2,950,952 discloses preparation of molecular sieve type T, which has been shown to be an intergrowth of ERI and OFF [J.M. Bennet et al., Nature, 1967, 214, 1005-1006.
  • US Patent 3,699,139 discloses synthesis of ERI/OFF using trimethylben- zylammonium.
  • US Patent 4,086,186 discloses synthesis of ZSM-34, which is also an intergrowth of ERI and OFF.
  • US Patent 4,503,023 discloses synthesis of LZ-220, which is a slightly more siliceous form of molecular sieve type T and also an intergrowth.
  • DABCO(I) and DABCO(II) has also been reported to give intergrowths of ERI and OFF [M. L. Ocelli et al., Zeolites, 1987, 7, 265-271 ].
  • SSZ-98 Another ERI molecular sieve designated SSZ-98 was reported in US Patent 9,409,786, 9,416,017 and US patent application 2016/0001273. This material is also essentially free of OFF intergrowth.
  • SSZ-98 is claimed to have a Si02/AI203 ratio between 15 and 50 with a rod-like or plate crystal morphology and it is prepared using N,N'-dimethyl-1 ,4-diazobicy- clo[2.2.2]octane dication as a structure directing agent.
  • a parameter (r c I r a ) is defined, which describes the ratio between the different dimensions along (r c ) and orthogonal (r a ) to the unique c-axis of the prepared crystallites e.g. determined by electron microscopy meth- ods (for hexagonal crystals the unique c-axis is parallel to the six-fold symmetry axis). Crystallite morphologies will be described using the words plate, tabular, prismatic, needle and rod-like. The relationship between these descriptions and r c I r a values is defined in the Table below
  • the present invention is in a first aspect a catalyst com- prising a molecular sieve with the ERI framework type having a mole ratio of silica-to- alumina from about 8 to about 100 and a crystal morphology defined by the ratio between the dimensions r c along and r a orthogonal to the unique c-axis between 0.5 and 2.0.
  • the crystal morphology of the novel ERI-molecular sieve with an r c /r a ratio of between 0.5 and 2 has a prismatic to tabular crystal morphology as shown in Figure 2 and 4 in the drawings, which is different to a rod-like or plate crystal morphology of the known ERI-molecular sieve SSZ-98. Specific features and embodiments of the invention are described below.
  • the calcined form of the ERI molecular sieve has a powder X-ray diffraction pattern collected in Bragg-Brentano geometry with a variable divergence slit using Cu K-alpha radiation essentially as shown in the following Table:
  • the silica-to-alumina mole ratio is between 8 and 100, preferably between 10 and 60.
  • At least a part of the aluminum and/or silicon in the molecular sieve is substituted by one or more metals selected from tin, zirconium, titanium, hafnium, germanium, boron, iron, indium and gallium.
  • the molecular sieve further contains copper and/or iron.
  • the one or more metals can be introduced into and/or on the molecular sieve product by ion-exchange, impregnation, solid-state procedures and precipitation on surface of the ERI-molecular sieve.
  • a further aspect of the present invention is a method for the conversion of nitrogen ox- ides to nitrogen in the presence of a reductant comprising the step of contacting the nitrogen oxides and the reductant with the catalyst according to any one of the above disclosed embodiments.
  • the reductant comprises hydrocarbons and/or ammonia or a precursor thereof.
  • the nitrogen oxides are contained in engine exhaust.
  • the nitrogen oxides are contained in exhaust from a gas turbine.
  • the nitrogen oxides comprise nitrous oxide.
  • Another aspect of the invention is a method for the selective oxidation of ammonia to nitrogen comprising the step of contacting the ammonia or a gas comprising the ammonia with the catalyst according to any one of the above disclosed embodiments.
  • the catalyst comprises an oxidation functionality or an oxidation catalyst.
  • the catalyst is arranged downstream of a selective catalytic reduction catalyst and wherein an excess of ammonia is used to reduce nitrogen oxides.
  • a further aspect of the invention method for the simultaneous oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides comprising the step of contacting the hydrocarbons, carbon monoxide and the nitrogen oxides with a catalyst according to any one of the above disclosed embodiments.
  • the catalyst further comprises one or more platinum group metals.
  • a further aspect of the invention is a method for the conversion of oxygenates to hydrocarbons comprising the step of contacting the oxygenates with a catalyst according to any one of the above disclosed embodiments.
  • the produced hydrocarbons comprise olefins.
  • a further aspect of the invention is a method for partial oxidation of methane to metha- nol and/or dimethyl ether comprising the step of contacting the methane with a catalyst according to any one of the above disclosed embodiments.
  • a further aspect of the invention is a method for the for the preparation of lower amines by reaction of ammonia with methanol with a catalyst according to any one of the above disclosed embodiments.
  • the ERI molecular sieve comprised in the catalyst of the invention can be prepared by a method comprising the steps of
  • a synthesis mixture comprising at least one source of silica and at least one source of alumina, or a combined source of both silica and alumina, a source of alkali or earth alkali (A), at least one OSDA being a cyclohexane-1 ,4-bis(trialkylammo- nium) cation, and water in molar ratios of:
  • the source of silica can comprise silica, fumed silica, silicic acid, amorphous or crystalline silicates, colloidal silica, tetraalkyl orthosilicates and mixtures thereof.
  • the source of alumina can comprise alumina, boehmite, aluminates and mixtures thereof.
  • a combined source of silica and alumina can be co-precipitated amorphous silica-alumina, kaolin, mesoporous materials, crystalline microporous aluminosilicates and mixtures thereof.
  • the OSDA is selected from the group consisting of cyclohexane-1 ,4-bis(tri- methylammonium), cyclohexane-1 ,4-bis(triethylammonium), cyclohexane-1 ,4-bis(ethyl- dimethylammonium), cyclohexane-1 ,4-bis(diethylmethylammonium).
  • OSDA cyclohexane-1 ,4-bis(trimethylammonium).
  • the OSDA cation is associated with anions, which typically can be hydroxide, chloride, bromide, iodide etc. as long as they are not detrimental to the formation of the molecular sieve.
  • tetravalent elements can also be introduced into the synthesis mixture. Such elements include tin, zirconium, titanium, hafnium, germanium and combinations thereof. Trivalent elements can also be included into the synthesis mixture either together with aluminium or without the presence of aluminium. Such trivalent elements include boron, iron, indium, gallium and combinations thereof. Both tetravalent and trivalent elements may be added in the form of metals, salts, oxides, sulphides and combinations thereof.
  • Transition metals may be included in the synthesis mixture either as simple salts or as complexes that protects the transition metal from precipitation under the caustic conditions dictated by the synthesis mixture.
  • polyamine complexes are useful for protecting transition metal ions of copper and iron during preparation and can also act to direct the synthesis towards specific molecular sieves (see for example the use of polyamines in combination with copper ions in US Patent application 2016271596). In such a way, transition metal ions can be introduced into the interior of the molecular sieve already during crystallization.
  • the synthesis mixture can also contain inexpensive pore-filling agents that can help in the preparation of more siliceous products.
  • pore filling agents can be crown- ethers (for example 18-crown-6), simple amines (for example trimethyl- and triethyl- amine) and other uncharged molecules.
  • Crystallization of the synthesis mixture to form the novel molecular sieve is performed at elevated temperatures until the molecular sieve is formed.
  • Hydrothermal crystallization is usually conducted in a manner to generate an autogenous pressure at temperatures from 100-200°C in an autoclave and for periods of time between two hours and 20 days.
  • the synthesis mixture can be subjected to stirring during the crystallization.
  • the resulting solid molecular sieve product is separated from the remaining liquid synthesis mixture by conventional separation techniques such as decantation, (vacuum-)filtration or centrifugation.
  • the recovered solids are then typically rinsed with water and dried using conventional methods (e.g. heating to 75-150°C under atmospheric pressure, vacuum drying or freeze-drying etc.) to obtain the 'as-synthesized' molecular sieve.
  • the 'as-synthesized' product refers herein to the molecular sieve after crystallization and prior to removal of the structure directing agent(s) or other organic additives.
  • the calcined form of the molecular sieve has a powder X-ray diffraction pattern collected in Bragg-Brentano geometry with a variable divergence slit using Cu K-alpha radiation essentially as shown in the following Table:
  • alkali or earth alkali ions e.g. Na +
  • lon-exchange with ammonium and/or hydrogen are well recognized methods to obtain the NhU-form or H-form of the molecular sieve.
  • Desired metal ions may also be included in the ion-exchange procedure or carried out separately.
  • the NhU-form of the material may also be converted to the H-form by simple heat treatment in a similar manner as described above.
  • the chemical composition of the ob- tained molecular sieve such as altering the silica-to-alumina molar ratio.
  • acid leaching inorganic and organic using complexing agents such as EDTA etc. can be used
  • steam-treatment de- silication and combinations thereof or other methods of demetallation can be useful in this case.
  • metals can be introduced into the novel molecular sieve to obtain a metal-substituted, metal-impregnated or metal-exchanged molecular sieve.
  • Metal ions may be introduced by ion-exchange, impregnation, solid-state procedures and other known techniques. Metals can be introduced to yield essentially atomically dispersed metal ions or be introduced to yield small clusters or nanoparticles with either ionic or metallic character. Alternatively, metals can simply be precipitated on the surface and in the pores of the molecular sieve. In the case where nanoparticles are preferred, consecutive treatment in e.g. a reductive atmosphere can be useful. In other cases, it may also be desirable to calcine the material af- ter introduction of metals or metal ions.
  • the molecular sieve according to the invention is particularly useful in heterogeneous catalytic conversion reactions, such when the molecular sieve catalyzes the reaction of molecules in the gas phase or liquid phase. It can also be formulated for other commercially important non-catalytic applications such as separation of gases.
  • the molecular sieve provided by the invention and from any of the preparation steps described above can be formed into a variety of physical shapes useful for specific applications.
  • the molecular sieve can be used in the powder form or shaped into pellets, extrudates or moulded monolithic forms, e.g. as full body corrugated substrate containing the molecular sieve.
  • the molecular sieve In shaping the molecular sieve, it will typically be useful to apply additional organic or inorganic components. For catalytic applications it is particularly useful to apply a com- bination with alumina, silica, titania, ceria, zirconia, various spinel structures or other oxides or combinations thereof. It may also be formulated with other active compounds such as active metals or other molecular sieves etc.
  • the molecular sieve can also be employed coated onto or introduced into a substrate that improves contact area, diffusion, fluid and flow characteristics of the gas stream.
  • the substrate can be a metal substrate, an extruded substrate or a corrugated substrate, the latter being made of ceramic paper.
  • the substrate can be designed as a flow-through or a wall-flow design. In the latter case, the gas flows through the walls of the substrate, and in this way, it can also contribute with an additional filtering effect.
  • the molecular sieve is typically present on or in the substrate in amounts between 10 and 600 g/L, preferably 100 and 300 g/L, as calculated by the weight of the molecular sieve per volume of the total catalyst article.
  • the molecular sieve is coated on or into the substrate using known wash-coating techniques. In this approach the molecular sieve powder is suspended in a liquid media together with binder(s) and stabilizer(s). The wash coat can then be applied onto the surfaces and walls of the substrate.
  • the wash coat optionally also contains binders based on T1O2, S1O2, AI2O3, ZrC>2, CeC>2 and combinations thereof.
  • the molecular sieve can also be applied as one or more layers on the substrate in combination with other catalytic functionalities or other zeolite catalysts.
  • One specific combination is a layer with an oxidation catalyst containing for example platinum or palladium or combinations thereof.
  • the molecular sieve can be additionally applied in limited zones along the gas-flow-direction of the substrate.
  • the molecular sieve according to the invention can be used in the catalytic conversion of oxides of nitrogen, typically in the presence of oxygen.
  • the molecular sieve can be used in the selective catalytic reduction (SCR) of oxides of nitrogen with a reductant such as ammonia and precursors thereof, including urea, or hydrocarbons.
  • SCR selective catalytic reduction
  • the molecular sieve will typically be loaded with a transition metal such as copper or iron or combinations thereof, using any of the procedures described above, in an amount sufficient to catalyse the specific reaction.
  • a certain amount of alkali or earth alkali can be beneficial. See for example a description of alkali and earth alkali effects on copper promoted CHA in [F. Gao, Y. Wang, N. M. Washton, M. Kollar, J. Szanyi, C. H. F. Peden, ACS Catal. 2015, 5, 6780-6791 ]. In other aspects, it may be preferred to use the molecular sieve essentially free of alkali or earth alkali.
  • the ERI molecular sieve according to the invention can advantageously be used as catalyst in the reduction of nitrogen oxides in the exhaust coming from a vehicular (i.e. mo- bile) internal combustion engine.
  • the exhaust system can comprise one or more of the following components: a diesel oxidation catalyst (DOC), a diesel particulate filter (DPF), a selective catalytic reduction catalyst (SCR) and/or an ammonia slip catalyst (ASC).
  • DOC diesel oxidation catalyst
  • DPF diesel particulate filter
  • SCR selective catalytic reduction catalyst
  • ASC ammonia slip catalyst
  • Such a system typically also contains means for metering the reductant as well as the possibility to meter hydrocarbons into the exhaust system upstream the SCR and DOC, respectively.
  • the ERI catalyst is arranged downstream and/or upstream of a Diesel oxidation catalyst. In another embodiment, the ERI catalyst is arranged upstream of an ammonia slip catalyst.
  • the ERI catalyst is arranged upstream and/or downstream of a diesel particulate filter
  • the SCR catalyst comprises the ERI molecular sieve of the invention.
  • the SCR catalyst may also contain other active components such as other molecular sieves. When the SCR catalyst is located in such an exhaust system it is exposed to high temperatures either from the engine or during thermal regeneration of one or more of the components in the system.
  • the SCR catalyst comprising the ERI molecular sieve
  • the SCR catalyst can be located between the DPF and the ASC components.
  • Another possi- bility is to arrange the SCR catalyst up-stream of the DOC, where some tolerance to unburnt hydrocarbons is required.
  • the SCR functionality may also be included in the DPF or combined with the ASC into a single component with a dual function.
  • the ERI molecular sieve according to the invention can also be part of an ammonia slip catalyst (ASC).
  • ASC catalyst is used in combination with the SCR article, and its function is to remove excess amount of ammonia, or a precursor thereof, that is needed in the SCR stage to remove high amounts of nitrogen oxides from the exhaust gas.
  • ASC-type catalysts are bifunctional catalysts.
  • the first function is oxidation of ammonia with oxygen, which produces NOx
  • the second function is NH3-SCR, in which NOx and residual amounts of ammonia react to nitrogen.
  • ASC catalysts consist of a combination of a component active for the oxidation of ammonia by oxygen and a component active for NH3-SCR.
  • ammonia slip catalysts based on the molecular sieve of the invention may also contain auxiliary materials, for example, and not limited to binders, support materials for the noble metal components, such as AI203, ⁇ 02, Si02. Such combinations can have different forms, such as a mixture of the ammonia oxidation component with the SCR-active form of the molecular sieve of the invention, reactors or catalyst items in series (See examples US patent 4,188,364).
  • the ammonia slip catalyst can be a washcoated layer of a mixture of the ammonia oxidation component with the SCR-active form of the ERI molecular sieve of the invention on a monolith, or a multi-layered arrangement washcoated on a monolith, in which the different layers contain different amounts of the ammonia oxidation component, or of the SCR-active form of the molecular sieve of the invention, or of any combination of the ammonia oxidation component and the SCR-active form of the molecular sieve of the invention (JP3436567, EP1992409).
  • ammonia oxidation component or the SCR-active form of the ERI molecular sieve of the invention or any combination of the ammonia oxidation component and the SCR-active form of the molecular sieve of the invention is present in walls of a monolith. This configuration can further be combined with different combina- tions of washcoated layers.
  • ASC catalyst is a catalyst article with a gas inlet end and a gas outlet end, in which the outlet end contains an ammonia oxidation component and the SCR-active form of the molecular sieve of the invention.
  • the inlet end of the catalyst article may then contain other functionalities.
  • the ERI molecular sieve of the invention is useful as catalyst in the reduction of nitrogen oxides in the exhaust gas from a gas turbine using ammonia as a reductant.
  • the catalyst may be arranged directly downstream from the gas turbine. It may also be exposed to large temperature fluctuations during gas turbine start-up and shutdown procedures.
  • the molecular sieve catalyst is used in a gas turbine system with a single cycle operational mode without any heat recovery system down-stream of the turbine.
  • the molecular sieve When placed directly after the gas turbine the molecular sieve is able to withstand exhaust gas temperatures up to 650°C with a gas composition containing water.
  • the molecular sieve of the invention is in a gas turbine exhaust treatment system in combination with a heat recovery system such as a Heat Recovery System Generator (HRSG).
  • HRSG Heat Recovery System Generator
  • the molecular sieve catalyst is arranged between the gas turbine and the HRSG.
  • the molecular sieve can be also arranged in several locations inside the HRSG.
  • Still an application of the ERI molecular sieve according to invention is the employment as catalyst in combination with an oxidation catalyst for the abatement of hydrocarbons and carbon monoxide in exhaust gas.
  • the oxidation catalyst typically composed of precious metals, such as Pt and Pd, can e.g. be arranged either up-stream or down-stream of the molecular sieve and both inside and outside of the HRSG.
  • the oxidation functionality can also be combined with the molecular sieve catalyst into a single catalytic unit.
  • the oxidation functionality may be combined directly with the molecular sieve by using the molecular sieve as support for the precious metals.
  • the precious metals can also be supported onto another support material and physically mixed with the molecular sieve.
  • the molecular sieve of to the invention is capable of removing nitrous oxide. It can for example be arranged in combination with a nitric acid production loop in a primary, sec- ondary or a tertiary abatement setup. In such an abatement process, the molecular sieve can be used to remove nitrous oxide as well as nitrogen oxides as separate catalytic articles or combined into a single catalytic article.
  • the nitrogen oxide may be used to facilitate the removal of the nitrous oxide.
  • Ammonia or lower hydrocarbons, including methane, may also be added as a reductant to further reduce nitrogen oxides and/or nitrous oxide.
  • the ERI molecular sieve of the invention can also be used in the conversion of oxygenates into various hydrocarbons.
  • the feedstock of oxygenates is typically lower alcohols and ethers containing one to four carbon atoms and/or combinations thereof.
  • the oxygenates can also be carbonyl compounds such as aldehyde, ketones and carboxylic acids. Particularly suitable oxygenate compounds are methanol, dimethyl ether, and mixtures thereof.
  • Such oxygenates can be converted into hydrocarbons in presence of the molecular sieve. In such a process the oxygenate feedstock is typically diluted and the temperature and space velocity is controlled to obtain the desired product range.
  • a further use of the molecular sieve of the invention is as catalyst in the production of lower olefins, in particular olefins suitable for use in gasoline or as catalyst in the produc- tion of aromatic compounds.
  • the ERI molecular sieve is typically used in its acidic form and will be extruded with binder materials or shaped into pellets together with suitable matrix and binder materials as described above.
  • Suitable active compounds such as metals and metal ions may also be included to change the selectivity towards the desired product range.
  • the ERI molecular sieve according to the invention can further be used in the partial oxidation of methane to methanol or other oxygenated compounds such as dimethyl ether.
  • W01 1046621 A1 One example of a process for the direct conversion of methane into methanol at temperatures below 300°C in the gas phase is provided in W01 1046621 A1.
  • the molecular sieve of the invention is loaded with an amount of copper sufficient to carry out the conversion.
  • the molecular sieve will be treated in an oxidizing atmosphere where-after methane is subsequently passed over the activated molecular sieve to directly form methanol. Subsequently, methanol can be extracted by suitable methods and the active sites regenerated by another oxidative treatment.
  • the ERI molecular sieve of the invention can be used to separate various gasses. Examples include the separation of carbon dioxide from natural gas and lower alcohols from higher alcohols. Typically, the practical application of the molecular sieve will be as part of a membrane for this type of separation.
  • the ERI molecular sieve of the invention can further be used in isomerization, cracking hydrocracking and other reactions for upgrading oil.
  • the ERI molecular sieve of the invention may also be used as a hydrocarbon trap e.g. from cold-start emissions from various engines.
  • the molecular sieve can be used for the preparation of small amines such as methyl amine and dimethylamine by reaction of ammonia with methanol.
  • the ERI catalyst can be coated on a monolith or on a corrugated substrate or be in form of an extrudate.
  • the dried solid product had a Si02/AI203 ratio of 9.8 determined by ICP-AES analysis.
  • the as-synthesized product is seen to be phase- pure ERI.
  • SEM analysis further reveals a tabular to prismatic crystal morphology.
  • the as-synthesized product is seen to be phase- pure ERI.
  • the measured diffractogram for the as-synthesized product is shown in Figure 1 .
  • SEM analysis further reveals a tabular crystal morphology (see
  • FIG. 1 SEM micrograph of the as-prepared molecular sieve prepared in Example 4.
  • Example 5 Synthesis of ERI
  • the dried solid product had a Si02/AI203 ratio of 22.0 determined by ICP-AES analysis.
  • the as-synthesized product is seen to be phase-pure ERI.
  • the measured diffractogram for the as-synthesized product is shown in Figure 3.
  • SEM analysis further reveals a prismatic crystal morphology (see Figure 4).
  • Figure 3 XRPD of the as-prepared molecular sieve prepared in Example 5.
  • Figure 4 SEM micrograph of the as-prepared molecular sieve prepared in Example 5.

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Abstract

La présente invention concerne un catalyseur qui comprend un tamis moléculaire avec un type de structure ERI ayant un rapport molaire de la silice sur l'alumine d'environ 8 à environ 100 et une morphologie cristalline définie par le rapport entre les dimensions r c de long de et r a orthogonale à l'axe c unique entre 0,5 et 2,0 et l'utilisation du catalyseur dans des réactions catalytiques.
PCT/EP2018/073601 2017-09-07 2018-09-03 Catalyseur comprenant un nouveau tamis moléculaire appartenant à la famille des eri et utilisation du catalyseur Ceased WO2019048375A1 (fr)

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