WO2019048373A1 - Method for preparation of a novel eri-molecular sieve - Google Patents

Method for preparation of a novel eri-molecular sieve Download PDF

Info

Publication number
WO2019048373A1
WO2019048373A1 PCT/EP2018/073599 EP2018073599W WO2019048373A1 WO 2019048373 A1 WO2019048373 A1 WO 2019048373A1 EP 2018073599 W EP2018073599 W EP 2018073599W WO 2019048373 A1 WO2019048373 A1 WO 2019048373A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular sieve
bis
cyclohexane
method
eri
Prior art date
Application number
PCT/EP2018/073599
Other languages
French (fr)
Inventor
Cristian-Renato BORUNTEA
Peter N. R. VENNESTRØM
Lars Fahl LUNDEGAARD
Avelino Corma CANÓS
Original Assignee
Haldor Topsøe A/S
Universitat Politècnica De València
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to ESP201731089 priority Critical
Priority to ES201731089A priority patent/ES2703220A1/en
Application filed by Haldor Topsøe A/S, Universitat Politècnica De València filed Critical Haldor Topsøe A/S
Publication of WO2019048373A1 publication Critical patent/WO2019048373A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/30Erionite or offretite type, e.g. zeolite T
    • C01B39/305Erionite or offretite type, e.g. zeolite T using at least one organic template directing agent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/52Crystalline 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
    • B01J29/56Iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/026After-treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48Preparation 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
    • C07C29/50Preparation 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing or organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • C10G47/20Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/50Zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9413Processes characterised by a specific catalyst
    • B01D53/9418Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/42Addition of matrix or binder particles
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/40Particle morphology extending in three dimensions prism-like
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/90Other morphology not specified above
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22Higher olefins
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30Aromatics

Abstract

A method for the preparation of a molecular sieve product with the ERI framework type by use of cyclohexane-1,4-bis(trialkylammonium) dication as an organic structure directing agent (OSDA).

Description

Title: Method for preparation of a novel ERI-molecular sieve

The present invention relates to a method for the preparation of a novel molecular sieve with the ERI framework type.

In particular, the invention is a method for the preparation of a crystalline molecular sieve material belonging to the ERI framework family essentially without intergrowth of OFF, with a high silica-to-alumina ratio and a tabular to prismatic crystal morphology.

Zeolites are crystalline microporous materials formed by corner-sharing T04 tetrahedra (T = Si, Al, P, Ge, B, Ti, Sn, etc.), interconnected by oxygen atoms to form pores and cavities of uniform size and shape precisely defined by their crystal structure. Zeolites are also denoted "molecular sieves" because the pores and cavities are of similar size as small molecules. This class of materials has important commercial applications as absorbents, ion-exchangers and catalysts.

Zeolite molecular sieves are classified by the International Zeolite Association (IZA) according 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.

The term framework type or framework topology as used herein, 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 (ERI) 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)]. Several ways of preparing ERI by synthetic methods have been disclosed.

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. The use of 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 ].

As illustrated by the above references, preparation of ERI typically leads to intergrowths with OFF. These intergrowths cannot be considered pure ERI topologies and leads to different channel systems and distribution of cages within the zeolite materials compared to pure ERI, which all-together will influence the properties of this class of materials.

Only a few publications relate to the synthesis of ERI essentially free of OFF intergrowths. US Patent 7,344,694 reports the preparation of UZM-12, which is proposed to have a Si/AI ratio above 5.5 (= Si02/AI203 > 1 1 ). Practically carrying out the invention to achieve silica-to-alumina (Si02/AI203) ratios higher than 12.6 were not given in the examples. Furthermore, UZM-12 is prepared using a density-mismatch approach where nanocrystalline material with crystallites of 15 to 50 nm with a spheroidal to "rice- grain" crystal morphologies can be obtained. Especially nanocrystallites are difficult to separate from the crystallization liquor.

Recently, 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. Later patent applications also claim Ν,Ν-dimethylpiperidinium cations, 1 ,3-dicclohex- ylimidizalium cations and their combination in US Patent applications 2017/0088432, 2017/0073240 and 2016/0375428 respectively. It is commonly acknowledged in the art that the hydrothermal stability of aluminosilicate molecular sieves become higher when the Si02/AI203 molar ratio is increased. Consequently, there is a need to increase the Si02/AI203 molar ratios of the known ERI molecular sieve materials, in particular for applications where hydrothermal stability is an issue. Furthermore, it is also commonly acknowledged in the art that the crystal mor- phology has a large impact on the performance of the molecular sieve in catalytic applications. A description of the behavior of different crystal morphologies in zeolite catalysis can be found in [S. Teketel, L. F. Lundegaard, W. Skistad, S. M. Chavan, U. Ols- bye, K. P. Lillerud, P. Beato, S. Svelle, J. Catal. 2015, 327, 22-32]. Thus, there is also a need to prepare materials with specific morphologies for specific catalytic applica- tions.

To distinguish different crystal morphologies a parameter (rc I ra) is defined, which describes the ratio between the different dimensions along (rc) and orthogonal (ra) 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 rc I ra values is defined in the Table below

Figure imgf000004_0001

It is thus a general object of this invention, to provide an ERI-crystalline molecular sieve essentially free of OFF intergrowths, high Si02/AI203 molar ratios and crystal morphologies different to what is already known.

We have found that the use of a cyclohexane-1 ,4-bis(trialkylammonium) dication as an organic structure directing agent (OSDA) results in the successful achievement of pure ERI with high silica-to-alumina ratios of up to 100 and with crystal morphologies different to that of SSZ-98.

Pursuant to the above finding, the present invention provides a method for the prepara- tion of a molecular sieve product with the ERI framework type comprising the steps of i) preparing 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) dication, and water in molar ratios of:

Figure imgf000005_0001
ii) subjecting the mixture to conditions capable of crystallizing the molecular sieve; and iii) separating the molecular sieve product to obtain the as-synthesized molecular sieve. 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. In an embodiment of the invention, the molecular sieve product has in the as-synthesized and anhydrous state a composition with the molar ratios given in the table:

Component Broad range Preferred range

Si02 / AI203 8-100 10-60

OSDA / Si02 0.01 -0.6 0.02-0.2

A / Si02 0.01 -0.6 0.02-0.2

The OSDA is is a cyclohexane-1 ,4-bis(trialkylammonium)dication having the structures (R = alkyl group) as shown below.

Figure imgf000006_0001

Preferably, 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). Presently, the most preferred OSDA is 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. In an embodiment, the as-synthesized 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:

2-Theta (°) d-spacing (A) Relative peak area

7,80 11,32 M

9,82 9,00 W

11,92 7,42 w

13,53 6,54 w

14,26 6,21 w

15,64 5,66 M

16,75 5,29 M

18,07 4,91 w

19,57 4,53 M

19,71 4,50 S 20,74 4,28 S-VS

21,59 4,11 VS

23,55 3,77 VS

23,87* 3,73 W-M

23,97* 3,71 W-M

23,98* 3,71 S-VS

24,31 3,66 W

25,24 3,53 VS

26,47 3,36 W

27,26 3,27 S

27,54* 3,24 W-M

27,62* 3,23 W-M

28,40 3,14 W

28,75 3,10 M

29,04 3,07 W

29,75 3,00 W

29,84 2,99 W

*Peak intensities and letter assignment is uncertain because of significant peak overlap where the relative areas of the observed peaks in the 2-Theta range are shown according to: W = weak: 0-20%; M = medium: 20-40%; S = strong: 40-60% and VS = very strong: 60-100%. 2-Theta values are ± 0.20°

The organic OSDA cation still retained in the as-synthesized molecular sieve product is in most cases, unless used in the as-synthesized form, removed by thermal treatment in the presence of oxygen. The temperature of the thermal treatment should be suffi- cient to remove the organic molecules either by evaporation, decomposition, combustion or a combination thereof. Typically, a temperature between 150 and 750°C for a period of time sufficient to remove the organic molecule(s) is applied. A person skilled in the art will readily be able to determine a minimum temperature and time for this heat treatment. Other methods to remove the organic material(s) retained in the as-synthe- sized molecular sieve include extraction, vacuum-calcination, photolysis or ozone-treatment.

In an embodiment, the calcined form of the molecular sieve product 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: 2-Theta (°) d-spacing (A) Relative peak area

7,81 11,31 M

9,79 9,03 w

11,79 7,50 w

13,55 6,53 s

14,16 6,25 w

15,66 5,65 w

16,75 5,29 w

18,00 4,92 w

19,40 4,57 w

19,65 4,51 W-M

20,77 4,27 s-vs

21,61 4,11 M-S

23,59 3,77 M-S

23,74* 3,74 W-M

23,72* 3,75 W-M

23,95* 3,71 S-VS

24,33 3,65 W

25,01 3,56 VS

26,45 3,37 W

27,30 3,26 VS

27,44* 3,25 W-M

27,41* 3,25 W-M

28,44 3,14 M

28,55 3,12 S-VS

29,07 3,07 W

29,67 3,01 W

29,83 2,99 W

*Peak intensities and letter assignment is uncertain because of significant peak overlap where the relative areas of the observed peaks in the 2-Theta range are shown according to: W = weak: 0-20%; M = medium: 20-40%; S = strong: 40-60% and VS = very strong: 60-100%. 2-Theta values are ± 0.20°

The novel 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 rc along and ra orthogonal to the unique c-axis, between 0.5 and 2.0.

The crystal morphology of the novel ERI-molecular sieve with an rc/ra ratio of between 0.5 and 2 has a prismatic to tabular crystal morphology as shown in Figure 2 and 4 in the examples below, which is different to rod-like or plate crystal morphology of the known ERI-molecular sieve SSZ-98.

In a further embodiment, the silica-to-alumina mole ratio of the novel ERI molecular sieve is between 8 and 100, preferably between 10 and 60.

Other 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. Thus, in a further embodiment, at least a part of the aluminum in the alumina-source and/or silicon in the silica-source in the synthesis mixture is substituted by one or more elements selected from tin, zirconium, titanium, hafnium, germanium, boron, iron, indium and gallium. 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. Especially, 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. Such 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.

Once the crystallization has completed 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.

Usually it is desirable to remove the remaining alkali or earth alkali ions (e.g. Na+) from the molecular sieve essentially free of occluded organic molecules by ion-exchange or other known methods, 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.

In certain cases, it may also be desirable to alter the chemical composition of the ob- tained molecular sieve, such as altering the silica-to-alumina molar ratio. Without being bound by any order of the post-synthetic treatments, 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.

To promote specific catalytic applications certain 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 atmos- phere can be useful. In other cases, it may also be desirable to calcine the material after introduction of metals or metal ions.

Thus, in another embodiment, the method according to the invention comprises the further step of introducing copper and/or iron on or into the molecular sieve product.

The molecular sieve according to the invention is particularly useful in heterogeneous catalytic conversion reactions, such as 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. For example, 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. 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 combination 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. In particular, 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. For this type of application, 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. In certain aspects of the invention 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. mobile) internal combustion engine. In this application 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). Such a system typically also contains means for metering the reduct- ant as well as the possibility to meter hydrocarbons into the exhaust system upstream the SCR and DOC, respectively.

Preferably, 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.

In the exhaust system as described above, the SCR catalyst, comprising the ERI molecular sieve, can be located between the DPF and the ASC components. Another possibility 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). The 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, and the second function is NH3-SCR, in which NOx and residual amounts of ammonia react to nitrogen.

Hence, ASC catalysts consist of a combination of a component active for the oxidation of ammonia by oxygen and a component active for NH3-SCR. The most commonly applied components for the oxidation of ammonia by oxygen are based on metals like Pt, Pd, Rh, Ir, Ru, but transition metal oxides or a combination of metal oxides, for example oxides Ce, Ti, V, Cr, Mn, Fe, Co, Nb, Mo, Ta, W can also be used for this purpose. When such materials are combined with metal-loaded form of the molecular sieve of the invention having SCR activity, an ammonia slip catalyst is obtained.

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, ΤΊ02, 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).

In particular, 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 compo- nent, 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).

In another configuration, the 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 combinations of washcoated layers. Another configuration of the 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. In this application, 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. In certain applications, 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. When placed directly after the gas turbine the molecular sieve is able to with- stand exhaust gas temperatures up to 650°C with a gas composition containing water.

Further applications of the molecular sieve of the invention are in a gas turbine exhaust treatment system in combination with a heat recovery system such as a Heat Recovery System Generator (HRSG). In such a process design, 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 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, secondary 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 cata- lytic 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 production of aromatic compounds.

In the above applications, 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.

Other 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. 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. In such a process, the molecular sieve of the invention is loaded with an amount of copper sufficient to carry out the conversion. Typically, 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. Another example is disclosed in [K. Narsimhan, K. lyoki, K. Dinh, Y. Roman-Leshkov, ACS Cent. Sci. 2016, 2, 424-429] where an increase or a continuous production of methanol is achieved by addition of water to the reactant stream to continuously extract methanol without having to alter the conditions between oxidative treatments and methanol formation.

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.

Furthermore, the molecular sieve can be used for the preparation of small amines such as methyl amine and dimethylamine by reaction of ammonia with methanol.

EXAMPLES

Example 1 : Synthesis of cvclohexane-1 ,4-bis(trimethylammonium hydroxide) OSDA A mixture of 30 mL formic acid (89.5 wt. % aqueous solution), 6.1 g NaHCC>3, 5 g trans- 1 ,4-diaminocyclohexane (98% purity powder) and 14 mL formaldehyde (37 wt. %aque- ous solution) was refluxed until no visible evolution of CO2 was noticed. The synthesis mixture was vacuum distillated after 50 mL HCI (2 mol/L aqueous solution) was added, followed by the addition of an excess of NaOH and extraction 3 times with chloroform. The chloroform portions were combined and 8 mL of methyl iodide (99 wt. %) was added followed by mixing overnight. The obtained solid was dissolved in water and ion exchange to hydroxide form, using an ion exchange resin.

Example 2: Synthesis of ERI

A mixture of 1.87 g cyclohexane-1 ,4-bis(trimethylammonium hydroxide)(12.7 wt. % aqueous solution), 1.7 g KOH (10 wt. % aqueous solution), 0.48 g distilled water and 0.94 g co-precipitated amorphous silica-alumina (Si02/AI203 = 12) was prepared. The mixture was heated in a closed Teflon lined autoclave at 135°C for 7 days and the solid product separated by filtration and washing with deionized water.By X-ray powder diffraction analysis, the as-synthesized product is seen to be phase-pure ERI.

Example 3: Synthesis of ERI

A mixture of 1.97 g cyclohexane-1 ,4-bis(trimethylammonium hydroxide)(12.7 wt. % aqueous solution), 1 .79 g KOH (10 wt. % aqueous solution), 0.46 g distilled water and 0.79 g FAU zeolite (Si02/AI203= 12) was prepared. The mixture was heated in a closed Teflon lined autoclave at 135°C for 7 days and the solid product separated by filtration and washing with deionized water.

The dried solid product had a Si02/AI203 ratio of 9.8 determined by ICP-AES analysis. By X-ray powder diffraction analysis, the as-synthesized product is seen to be phase- pure ERI. SEM analysis further reveals a tabular to prismatic crystal morphology.

Example 4: Synthesis of ERI

A mixture of 1.95 g cyclohexane-1 ,4-bis(trimethylammonium hydroxide)(12.7 wt. % aqueous solution), 1 .77 g KOH (10 wt. % aqueous solution), 0.5 g distilled water and 0.79 g co-precipitated amorphous silica-alumina (Si02/AI203 = 30) was prepared. The mixture was heated in a closed Teflon lined autoclave at 135°C for 7 days and the solid product separated by filtration and washing with deionized water.

By X-ray powder diffraction analysis, 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 Figure 2).

Figure 1 XRPD of the as-prepared molecular sieve prepared in Example 4.

Figure 2 SEM micrograph of the as-prepared molecular sieve prepared in Example 4. Example 5: Synthesis of ERI

A mixture of 1.99 g cyclohexane-1 ,4-bis(trimethylammonium hydroxide)(12.7 wt. % aqueous solution), 1 .81 g KOH (10 wt. % aqueous solution), 0.45 g distilled water and 0.74 g FAU zeolite (Si02/AI203= 30) was prepared. The mixture was heated in a closed Teflon lined autoclave at 135°C for 7 days and the solid product separated by filtration and washing with deionized water.

The dried solid product had a Si02/AI203 ratio of 22.0 determined by ICP-AES analysis. By X-ray powder diffraction 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.

Calcination of the dried as-prepared molecular sieve was carried out at 550°C for 3h. Afterwards the calcined product was ion-exchanged with NH4+. The measured X-ray diffractogram for the calcined product is shown in Figure 5. Furthermore, N2-physisorp- tion revealed a multipoint BET surface area of 559 m2/g and a micropore volume of 0.19 cm3/g, clearly indicating the microporous nature of the prepared material.

Figure 5 XRPD of the calcined molecular sieve prepared in Example 5.

Claims

Claims
1 . A method for the preparation of a molecular sieve product with the ERI framework type comprising the steps of i) preparing 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:
Figure imgf000020_0001
ii) subjecting the mixture to conditions capable of crystallizing the molecular sieve; and iii) separating the molecular sieve product to obtain the as-synthesized molecular sieve.
2. The method of claim 1 , wherein molecular sieve product has in the as-synthe- sized and anhydrous state a composition with the molar ratios given in the following Table:
Component Broad range Preferred range
Si02 / AI203 8-100 10-60
OSDA / Si02 0.01 -0.6 0.02-0.2
A / Si02 0.01 -0.6 0.02-0.2 where the OSDA is is a cyclohexane-1 ,4-bis(trialkylammonium) dication and A is an alkali or earth alkali cation.
3. The method of claim 1 or 2, wherein the cyclohexane-1 ,4-bis(trialkylammonium) dication is selected from the group consisting of cyclohexane-1 ,4-bis(trimethylammo- nium), cyclohexane-1 ,4-bis(triethylammonium), cyclohexane-1 ,4-bis(ethyldime- thylammonium), cyclohexane-1 ,4-bis(diethylmethylammonium). 4. The method of claim 1 or 2, wherein the cyclohexane-1 ,4-bis(trialkylammonium) dication is cyclohexane-1 ,
4-bis(trimethylammonium).
5. The method of any one of claims 1 to 4, wherein the as-synthesized 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:
Figure imgf000021_0001
*Peak intensities and letter assignment is uncertain because of significant peak overlap where the relative areas of the observed peaks in the 2-Theta range are shown according to: W = weak: 0-20%; M = medium: 20-40%; S = strong: 40-60% and VS = very strong: 60-100%.2-Theta values are ± 0.20°.
6. The method of any one of claims 1 to 5 comprising the further step of calcining the molecular sieve product and wherein the calcined form of the molecular sieve product 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:
Figure imgf000022_0001
*Peak intensities and letter assignment is uncertain because of significant peak overlap where the relative areas of the observed peaks in the 2-Theta range are shown according to: W = weak: 0-20%; M = medium: 20-40%; S = strong: 40-60% and VS = very strong: 60-100%. 2-Theta values are ± 0.20°.
7. The method of any one of claims 1 to 6, wherein the silica-to-alumina mole ratio of the molecular sieve is between 8 and 100.
8. The method of any one of claims 1 to 6, wherein the silica-to-alumina mole ratio of the molecular sieve is between 10 and 60.
9. The method of any one of claims 1 to 8, wherein at least a part of the aluminum in the alumina-source and/or silicon in the silica-source in the synthesis mixture is substituted by one or more elements selected from tin, zirconium, titanium, hafnium, germanium, boron, iron, indium and gallium.
10. The method of any one of claims 1 to 9, comprising the further step of introducing copper and/or iron on or into the molecular sieve product.
PCT/EP2018/073599 2017-09-07 2018-09-03 Method for preparation of a novel eri-molecular sieve WO2019048373A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ESP201731089 2017-09-07
ES201731089A ES2703220A1 (en) 2017-09-07 2017-09-07 Method for the preparation of a new ERI molecular sieve

Publications (1)

Publication Number Publication Date
WO2019048373A1 true WO2019048373A1 (en) 2019-03-14

Family

ID=63528730

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/073599 WO2019048373A1 (en) 2017-09-07 2018-09-03 Method for preparation of a novel eri-molecular sieve

Country Status (2)

Country Link
ES (1) ES2703220A1 (en)
WO (1) WO2019048373A1 (en)

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950952A (en) 1958-05-08 1960-08-30 Union Carbide Corp Crystalline zeolite t
US3699139A (en) 1969-10-16 1972-10-17 Mobil Oil Corp Synthetic crystalline aluminosilicate
US4086186A (en) 1976-11-04 1978-04-25 Mobil Oil Corporation Crystalline zeolite ZSM-34 and method of preparing the same
US4188364A (en) 1977-05-31 1980-02-12 Caterpillar Tractor Co. Two-stage catalysis of engine exhaust
US4503023A (en) 1979-08-14 1985-03-05 Union Carbide Corporation Silicon substituted zeolite compositions and process for preparing same
JP3436567B2 (en) 1993-06-23 2003-08-11 バブコック日立株式会社 An exhaust gas purifying catalyst and a manufacturing method thereof
US20060073094A1 (en) * 2004-10-06 2006-04-06 Miller Mark A UZM-12 and UZM-12 HS: crystalline aluminosilicate zeolitic compositions and processes for preparing and using the compositions
EP1992409A1 (en) 2007-05-09 2008-11-19 N.E. Chemcat Corporation Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same
WO2011046621A1 (en) 2009-10-14 2011-04-21 The Board Of Trustees Of The Leland Stanford Junior University Low temperature direct selective methane to methanol conversion
US20160001273A1 (en) 2014-07-03 2016-01-07 Chevron U.S.A. Inc Processes using molecular sieve ssz-98
US9409786B2 (en) 2014-07-03 2016-08-09 Chevron U.S.A. Inc. Molecular sieve SSZ-98
US9416017B2 (en) 2014-07-03 2016-08-16 Chevron U.S.A. Inc. Method for making molecular sieve SSZ-98
US20160271596A1 (en) 2012-12-12 2016-09-22 Haldor Topsoe A/S One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof
US20160375428A1 (en) 2015-06-29 2016-12-29 Chevron U.S.A. Inc. Synthesis of aluminosilicate zeolite ssz-98
US20170073240A1 (en) 2015-09-11 2017-03-16 Chevron U.S.A. Inc. Method for preparing zeolite ssz-98
US20170088432A1 (en) 2015-09-25 2017-03-30 Chevron U.S.A. Inc. Method for preparing zeolite ssz-98

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950952A (en) 1958-05-08 1960-08-30 Union Carbide Corp Crystalline zeolite t
US3699139A (en) 1969-10-16 1972-10-17 Mobil Oil Corp Synthetic crystalline aluminosilicate
US4086186A (en) 1976-11-04 1978-04-25 Mobil Oil Corporation Crystalline zeolite ZSM-34 and method of preparing the same
US4188364A (en) 1977-05-31 1980-02-12 Caterpillar Tractor Co. Two-stage catalysis of engine exhaust
US4503023A (en) 1979-08-14 1985-03-05 Union Carbide Corporation Silicon substituted zeolite compositions and process for preparing same
JP3436567B2 (en) 1993-06-23 2003-08-11 バブコック日立株式会社 An exhaust gas purifying catalyst and a manufacturing method thereof
US20060073094A1 (en) * 2004-10-06 2006-04-06 Miller Mark A UZM-12 and UZM-12 HS: crystalline aluminosilicate zeolitic compositions and processes for preparing and using the compositions
US7344694B2 (en) 2004-10-06 2008-03-18 Uop Llc UZM-12 and UZM-12HS: crystalline aluminosilicate zeolitic compositions and processes for preparing and using the compositions
EP1992409A1 (en) 2007-05-09 2008-11-19 N.E. Chemcat Corporation Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same
WO2011046621A1 (en) 2009-10-14 2011-04-21 The Board Of Trustees Of The Leland Stanford Junior University Low temperature direct selective methane to methanol conversion
US20160271596A1 (en) 2012-12-12 2016-09-22 Haldor Topsoe A/S One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof
US20160001273A1 (en) 2014-07-03 2016-01-07 Chevron U.S.A. Inc Processes using molecular sieve ssz-98
US9409786B2 (en) 2014-07-03 2016-08-09 Chevron U.S.A. Inc. Molecular sieve SSZ-98
US9416017B2 (en) 2014-07-03 2016-08-16 Chevron U.S.A. Inc. Method for making molecular sieve SSZ-98
US20160375428A1 (en) 2015-06-29 2016-12-29 Chevron U.S.A. Inc. Synthesis of aluminosilicate zeolite ssz-98
US20170073240A1 (en) 2015-09-11 2017-03-16 Chevron U.S.A. Inc. Method for preparing zeolite ssz-98
US20170088432A1 (en) 2015-09-25 2017-03-30 Chevron U.S.A. Inc. Method for preparing zeolite ssz-98

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
CH. BAERLOCHER; L.B. MCCUSKER; D.H. OLSON: "Atlas of Zeolite Framework Types", 2007
F. GAO; Y. WANG; N. M. WASHTON; M. KOLLAR; J. SZANYI; C. H. F. PEDEN, ACS CATAL., vol. 5, 2015, pages 6780 - 6791
J.M. BENNET ET AL., NATURE, vol. 214, 1967, pages 1005 - 1006
JIE ZHU ET AL: "Ultrafast synthesis of high-silica erionite zeolites with improved hydrothermal stability", CHEMICAL COMMUNICATIONS, vol. 53, no. 50, 24 May 2017 (2017-05-24), pages 6796 - 6799, XP055513320, ISSN: 1359-7345, DOI: 10.1039/C7CC03166A *
JOO HYUCK LEE ET AL: "Supporting info for Synthesis and Characterization of ERI-Type UZM-12 Zeolites and their Methanol-to-Olefin Performance", ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, 22 September 2010 (2010-09-22), Chichester, UK, pages 596 - 605, XP055513517, Retrieved from the Internet <URL:https://pubs.acs.org/doi/suppl/10.1021/ja105185r/suppl_file/ja105185r_si_001.pdf> [retrieved on 20181009], DOI: 10.1002/apj.453 *
JOO HYUCK LEE ET AL: "Synthesis and Characterization of ERI-Type UZM-12 Zeolites and their Methanol-to-Olefin Performance", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, US, vol. 132, no. 7, 22 September 2010 (2010-09-22), pages 12971 - 12982, XP002668581, ISSN: 0002-7863, [retrieved on 20100825], DOI: 10.1021/JA105185R *
K. NARSIMHAN; K. LYOKI; K. DINH; Y. ROMAN-LESHKOV, ACS CENT. SCI., vol. 2, 2016, pages 424 - 429
M. L. OCELLI ET AL., ZEOLITES, vol. 7, 1987, pages 265 - 271
MARTÍN NURIA ET AL: "Cage-based small-pore catalysts for NH3-SCR prepared by combining bulky organic structure directing agents with modified zeolites as reagents", APPLIED CATALYSIS B: ENVIRONMENTAL, ELSEVIER, AMSTERDAM, NL, vol. 217, 29 May 2017 (2017-05-29), pages 125 - 136, XP085112832, ISSN: 0926-3373, DOI: 10.1016/J.APCATB.2017.05.082 *
S. TEKETEL; L. F. LUNDEGAARD; W. SKISTAD; S. M. CHAVAN; U. OLS-BYE; K. P. LILLERUD; P. BEATO; S. SVELLE, J. CATAL., vol. 327, 2015, pages 22 - 32
SCHLENKER, J.L.; PLUTH, J.J.; SMITH, J.V., ACTA CRYSTALLOGR., vol. B33, 1977, pages 3265 - 3268
STAPLES, L.W.; GARD, J.A., MINERAL. MAG., vol. 32, 1959, pages 261 - 281

Also Published As

Publication number Publication date
ES2703220A1 (en) 2019-03-07

Similar Documents

Publication Publication Date Title
JP5261189B2 (en) Zeolite catalyst with improved NOx selective catalytic reduction efficiency
JP5743885B2 (en) Process for direct synthesis of Cu-containing zeolites with CHA structure
JP2011510899A (en) Catalysts, systems and methods utilizing non-zeolitic metals comprising molecular sieves having a CHA crystal structure
US9895684B2 (en) Process for the preparation of zeolites having CHA structure
Ye et al. Activity, propene poisoning resistance and hydrothermal stability of copper exchanged chabazite-like zeolite catalysts for SCR of NO with ammonia in comparison to Cu/ZSM-5
EP2269733A1 (en) Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34)
US9044744B2 (en) Catalyst for treating exhaust gas
DE69320195T3 (en) Synthesis of zeolite films that are bonded to substrates, structures and their uses
CN101827654B (en) Novel iron-containing aluminosilicate zeolites and methods of making and using same
KR20170083606A (en) Afx zeolite
JP6347913B2 (en) Method, catalyst, system and method for preparing a copper-containing molecular sieve with a CHA structure
JP4944038B2 (en) High silica molecular sieve CHA
JP5895510B2 (en) Chabazite-type zeolite and method for producing the same, low-silica zeolite supporting copper, nitrogen oxide reduction and removal catalyst containing the zeolite, and nitrogen oxide reduction and removal method using the catalyst
JP5238908B2 (en) Organic template-free synthesis process to produce zeolitic materials
JP2004509044A (en) Big and heteroatoms lattice substitution method in borosilicate zeolites oversized pores
KR101852143B1 (en) Novel metal - containing zeolite beta for nox reduction
JP6112568B2 (en) Synthesis of molecular sieve precursors and molecular sieves
CN102803143A (en) Organotemplate-free synthetic process for the production of a zeolitic material
CN103534210A (en) Beta-type iron silicate composition and method for reducing nitrogen oxides
JP5750701B2 (en) Copper-containing levite molecular sieve for selective reduction of NOx
JP5169779B2 (en) Nitrogen oxide purification catalyst and nitrogen oxide purification method
De-La-Torre et al. Cu-zeolite catalysts for NOx removal by selective catalytic reduction with NH3 and coupled to NO storage/reduction monolith in diesel engine exhaust aftertreatment systems
CN106470945B (en) Use the method for molecular sieve SSZ-98
KR20150074094A (en) Mixed metal 8-ring small pore molecular sieve catalyst compositions, catalytic articles, systems and methods
US20100111791A1 (en) Bimetallic Catalysts for Selective Ammonia Oxidation

Legal Events

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

Ref document number: 18766168

Country of ref document: EP

Kind code of ref document: A1