Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
• • 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
  • B01J29/82—Phosphates
  • B01J29/83—Aluminophosphates [APO compounds]
• • 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
  • B01J29/82—Phosphates
  • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
• • 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
  • B01J29/82—Phosphates
  • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
  • B01J29/85—Silicoaluminophosphates [SAPO compounds]
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
  • C01B37/04—Aluminophosphates [APO compounds]
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
  • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
  • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/54—Phosphates, e.g. APO or SAPO compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/62—Catalyst regeneration
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/08—Halides
  • B01J27/12—Fluorides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/82—Phosphates
  • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
  • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins
• • 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
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• This invention relates to the synthesis of sihcoaluminophosphate and aluminophosphate molecular sieves of the CHA framework type.
• the present invention relates to the synthesis of sihcoaluminophosphate molecular sieves of the CHA framework type having a low silicon to aluminium atomic ratio.
• Olefins are traditionally produced from petroleum feedstock by catalytic or steam cracking processes. These cracking processes, especially steam cracking, produce light olefin(s) such as ethylene and/or propylene from a variety of hydrocarbon feedstock. It has been known for some time that oxygenates, especially alcohols, e.g. methanol, are convertible into light olefin(s).
• oxygenates especially alcohols, e.g. methanol
• the preferred methanol conversion process is generally referred to as a methanol-to- olefin(s) process, where methanol is converted to primarily ethylene and propylene in the presence of a molecular sieve.
• SAPO molecular sieves for converting methanol to olefm(s) are the metalloaluminophosphates such as the silicoaluminophosphates (SAPO's).
• SAPO molecular sieves There are a wide variety of SAPO molecular sieves known in the art, of these the more important examples include SAPO-5, SAPO-11, SAPO-18, SAPO- 34, SAPO-35, SAPO-41, and SAPO-56.
• SAPO molecular sieves having the CHA framework and especially SAPO-34 are particularly important catalysts.
• the CHA framework type has a double six-ring structure in an ABC stacking arrangement.
• the pore openings of the structure are defined by eight member rings that have a diameter of about 4.0 A , and cylindrical cages within the structure of approximately 10 x 6.7 A ("Atlas of Zeolite Framework Types", 2001, 5th Edition, p. 96).
• Other SAPO molecular sieves of CHA framework type include SAPO-44, SAPO-47 and ZYT-6. [0004] The synthesis of SAPO molecular sieves is a complicated process.
• TEAOH tetraethylammonium hydroxide
• DPA dipropylamine
• DPA dimethyl methacrylate
• SAPO-20 was produced from synthesis mixtures containing tetramethylammonium hydroxide and fluoride ions from water soluble sources of fluoride such as Na, K and ammonium fluoride.
• Wilson et al. reported that it is beneficial to have lower Si content for methanol-to-olefins reaction (Microporous and Mesoporous Materials, 29, 117-126, 1999). Low Si content has the effect of reducing propane formation and decreasing catalyst deactivation.
• the Si/Al atomic ratio is often expressed as the number of Si atoms per CHA cage of the molecular sieve, each CHA cage being composed of 12 T atoms (T atoms are either Si, Al or P).
• T atoms are either Si, Al or P.
• Yet another separate objective is to find templates suitable under a wide range of molecular sieve synthesis conditions for the synthesis of sihcoaluminophosphate or aluminophosphate molecular sieves of CHA framework type.
• the present invention provides a process for preparing crystalline molecular sieve of CHA framework type, which process comprises: a) providing a synthesis mixture comprising a source of aluminum, a source of phosphorus, a source of silicon and at least one organic template of formula (I)
• R2 are independently selected from the group consisting of alkyl groups having from 1 to 3 carbon atoms and hydroxyalkyl groups having from 1 to 3 carbon atoms;
• R3 is selected from the group consisting of 4- to 8-membered cycloalkyl groups, optionally substituted by 1 to 3 alkyl groups having from 1 to 3 carbon atoms, 4- to 8-membered heterocyclic groups having from 1 to 3 heteroatoms, said heterocyclic groups being optionally substituted by 1 to 3 alkyl groups having from 1 to 3 carbon atoms and the heteroatoms in said heterocyclic groups being selected from the group consisting of O, N, and S; and b) inducing crystallization of crystalline molecular sieve of CHA framework type from the reaction mixture.
• the organic template of formula (I) is a template of formula (II)
• the organic template is selected from the group consisting of N,N-dimethyl-cyclohexylamine, N,N-dimethyl-methyl- cyclohexylamine, N,N-dimethyl-cyclopentylamine, N,N-dimethyl-methyl- cyclopentylamine, N,N-dimethyl-cycloheptylamine, N,N-dimethyl- methylcycloheptylamine, .
• the organic template is N,N-dimethyl- cy clohexylamine .
• the process of the present invention results molecular sieves having the CHA framework type which, as synthesized, have unique x-ray diffraction patterns.
• a sihcoaluminophosphate molecular sieve substantially of CHA framework type, comprising within its intra-crystalline structure at least one template of formula I, preferably of formula II, more preferably N,N-dimethyl-cyclohexylamine.
• the present invention provides a crystalline sihcoaluminophosphate molecular sieve substantially of CHA framework type, having a characteristic X-ray powder diffraction pattern containing at least the d- spacings as set forth in Table la:
• the present invention provides a crystalline sihcoaluminophosphate molecular sieve substantially of CHA framework type, having a characteristic X-ray powder diffraction pattern containing at least the d- spacings as set forth in Table lb:
• the molecular sieve having the X-ray diffraction pattern of Table la or lb comprises N,N-dimethylcyclohexylamine within its intra- crystalline structure.
• the present invention provides a crystalline sihcoaluminophosphate molecular sieve substantially of CHA framework type, having a characteristic X-ray powder diffraction pattern containing at least the d- spacings as set forth in Table Ilia:
• the present invention provides a crystalline sihcoaluminophosphate molecular sieve substantially of CHA framework type, having a characteristic X-ray powder diffraction pattern containing at least the d- spacings as set forth in Table Illb:
• the molecular sieve having the X-ray diffraction pattern of Table Ilia or Illb comprises N,N-dimethylcyclohexylamine within its intra-crystalline structure and fluoride, more preferably hydrogen fluoride.
• the present invention provides a method for the manufacture of a molecular sieve catalyst composition, which method comprises forming a mixture comprising at least one molecular sieve of the present invention, with at least one formulating agent, to form a molecular sieve catalyst composition.
• the present invention provides for a molecular sieve catalyst composition comprising at least one molecular sieve of the present invention in admixture with at least one formulating agent.
• the present invention provides for the use of a template of formula I, preferably of formula II, more preferably N,N- dimethylcyclohexylamine, optionally in the presence of a source of fluoride, in the synthesis of silicoaluminophosphates of CHA framework type.
• the present invention provides a method for the manufacture of a molecular sieve catalyst composition, which method comprises forming a mixture comprising at least one molecular sieve comprising within its intra-crystalline structure at least one template of formula I, preferably of formula II, more preferably N,N-dimethylcyclohexylamine, or as obtained from a process utilising a template of formula I, preferably of formula II, more preferably N,N-dimethylcyclohexylamine, with at least one formulating agent, to form a molecular sieve catalyst composition.
• the present invention provides for a molecular sieve catalyst composition
• a molecular sieve catalyst composition comprising at least one sihcoaluminophosphate molecular sieve comprising within its intra-crystalline structure at least one template of formula I, preferably of formula II, more preferably N,N-dimethylcyclohexylamine or as obtained from a process utilising a template of formula I, preferably of formula II, more preferably N,N- dimethylcyclohexylamine, in admixture with at least one formulating agent.
• the molecular sieves of the present invention or prepared according to the preparation method of the present invention are useful catalysts for the conversion of feedstocks, preferably oxygenate feedstocks, into one or more olefins.
• Figure 1 shows the XRD patterns of crystalline molecular sieves of
• FIG. 1 shows the XRD patterns of crystalline molecular sieves of
• CHA framework type comprising N,N-dimethylcyclohexylamine within their intra-crystalline structures obtained after 3 days of crystallization, using HF as well as varying amounts of silicon source in the molecular sieve synthesis mixture.
• the invention is primarily directed toward a method for synthesising crystalline aluminophosphates and silicoaluminophosphates substantially of the CHA framework type.
• a specific group of organic amines are effective templates in the synthesis of aluminophosphate and sihcoaluminophosphate molecular sieves of the CHA framework type.
• templates of formula (I), preferably of formula (II), most preferably, N,N-dimethylcyclohexylamine, as described below are used to prepare SAPO molecular sieves, then SAPOs of CHA framework type and of substantially high purity are obtained.
• these templates may be utilised for the synthesis of SAPOs of CHA framework type having low Si/Al atomic ratios, i.e. low acidity.
• the molecular sieves of the present invention may be represented by the empirical formula, on an anhydrous basis: mR:(Si x Al y P 2 )O 2 wherein R represents at least one templating agent of formula (I)
• R! is selected from the group consisting of alkyl groups or hydroxyalkyl groups
• R 2 is selected from the group consisting of alkyl groups or hydroxyalkyl groups
• R 3 is selected from the group consisting of cycloalkyl groups having from 4 to 8 carbon atoms, said cycloalkyl groups being optionally substituted by 1 to 3 alkyl groups, 4 to 8-membered heterocyclic groups having 1 to 3 heteroatoms, said heterocyclic groups being optionally substituted by 1 to 3 alkyl groups and the heteroatoms in said heterocyclic groups being selected from the group consisting of O, N, and S, all alkyl and alkoxy groups independently having from 1 to 3 carbon atoms; and m is the number of moles of R per mole of (Si JC Al y P z )O 2 and m has a value from 0.0417 to 0.3333, preferably from 0.0624 to 0.166, and most preferably from 0.0667 to 0.1 ; x, y, and
• m is greater than or equal to 0.04, x is greater than or equal to 0, and y and z are greater than or equal to 0.01.
• m is in the range of from greater than 0.01 to about 0.3333, x is in the range of from greater than 0 to about 0.31, y is in the range of from 0.25 to 1.0, and z is in the range of from 0.25 to 0.9, more preferably m is in the range of from 0.05 to 0.10, x is in the range of from 0.01 to 0.2, most preferably from 0.02 to 0.15, y is in the range of from 0.4 to 0.9, and z is in the range of from 0.3 to 0.9.
• the molecular sieve may also contain fluorine.
• the organic template is removed and the resulting aluminophosphates or silicoaluminophosphates have a CHA framework type and are of substantially high purity in terms of their framework type with little or no intergrowth with other sihcoaluminophosphate or aluminophosphate framework types.
• sihcoaluminophosphate substantially of CHA framework type or of substantially high purity in terms of its framework type it is meant a sihcoaluminophosphate molecular sieve which comprises 60% or greater of the CHA framework type, preferably 70% or greater of the CHA framework type, more preferably 90% or greater of the CHA framework type, and most preferably 95% or greater of the CHA framework type, as determined by XRD.
• the molecular sieves of the present invention may contain a small amount of intergrowth with another sihcoaluminophosphate or aluminophosphate molecular sieve.
• the molecular sieve can comprise at least one intergrown phase of AEI and CHA framework types.
• the calcined molecular sieve of the present invention has a Si/Al ratio of less than 0.167, preferably less than 0.134, more preferably less than 0.100.
• the Si/Al ratio in the molecular sieve is within the range of from 0 to 0.167, more preferably in the range of from 0.02 to 0.167, even more preferably in the range of from 0.03 to 0.134 and most preferably in the range of from 0.03 to 0.100.
• sihcoaluminophosphate and aluminophosphate molecular sieves are synthesized by the hydrothermal crystallization of one or more of a source of aluminium, a source of phosphorous, a templating agent (or template), and, optionally, a source of silicon.
• a combination of a source of aluminium, a source of phosphorous, one or more templating agents, optionally a source of silicon, and, optionally, one or more metal containing compounds are placed in a sealed pressure vessel, optionally lined with an inert plastic such as polytetrafluoroethylene, and heated, under a crystallization pressure and temperature, until a crystalline material is formed, and then recovered by filtration, centrifugation and/or decanting.
• a sealed pressure vessel optionally lined with an inert plastic such as polytetrafluoroethylene
• the phosphorous-, aluminium-, and optionally silicon- containing components are mixed, preferably while stirring and/or agitating and/or seeding with a crystalline material, optionally with an alkali metal, in a solvent such as water, and one or more templating agents, to form a synthesis mixture that is then heated under crystallization conditions of pressure and temperature as described in U.S. Patent Nos. 4,440,871 which is fully incorporated by reference.
• the template is used in an amount such that the molar ratio of template to alumina (Al 2 O 3 ) in the reaction mixture is within the range of from 0.6:1.0 to 3.0:1.0, preferably from 1.0:1.0 to 2.0:1.0.
• R! is selected from the group consisting of alkyl groups or hydroxyalkyl groups
• R 2 is selected from the group consisting of alkyl groups or hydroxyalkyl groups
• R 3 is selected from the group consisting of cycloalkyl groups having from 4 to 8 carbon atoms, said cycloalkyl groups being optionally substituted by 1 to 3 alkyl groups, 4 to 8-membered heterocyclic groups having 1 to 3 heteroatoms, said heterocyclic groups being optionally substituted by 1 to 3 alkyl groups and the heteroatoms in said heterocyclic groups being selected from the group consisting of O, N, an S, all alkyl and alkoxy groups independently having from 1 to 3 carbon atoms.
• the organic template of formula (I) is a template of formula (II)
• R 3 is selected from the group consisting of cycloalkyl groups, said cycloalkyl groups being optionally substituted by 1 to 3 methyl groups, and said cycloalkyl groups having from 4 to 8 carbon atoms, preferably 6 carbon atoms.
• the template of formula (I) or of formula II is selected from the group of templates of formula I or formula II in which R 3 is selected from the group consisting of cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, pentamethylcyclohexyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, trimethylcyclopentyl, tetramethylcyclopentyl, cycloheptyl, methylcycloheptyl, dimethylcycloheptyl, trimethylcycloheptyl, tetramethylcycloheptyl, pentamethylcycloheptyl, hexamethylcycloheptyl, and piperidinyl.
• the template is N,N-dimethylcyclohexylamine.
• the template of formula (I) or of formula (II) may be used in combination with one or more additional templates normally used in the manufacture of silicoaluminophosphates of CHA framework type.
• additional templates include: the group of tetraethylammonium compounds, such as tetraethylammonium hydroxide (TEAOH), tetraethylammonium phosphate, tetraethylammonium fluoride, tetraethylammonium bromide, tetraethylammonium chloride and tetraethylammonium acetate and also include DPA, isopropylamine, cyclohexylamine, morpholine, methylbutylamine, diethanolamine, and triethylamine.
• TEAOH tetraethylammonium hydroxide
• tetraethylammonium phosphate tetraethylam
• N,N-dimethylcyclohexylamine is used the resulting silicoaluminophosphates of CHA framework type have a Si per CHA cage ratio within the range of from 0.1 to 1.0, preferably of from 0.15 to 0.8 and more preferably of from 0.2 to 0.7.
• Si per CHA cage ratio within the range of from 0.1 to 1.0, preferably of from 0.15 to 0.8 and more preferably of from 0.2 to 0.7.
• silicoaluminophosphates of CHA framework type having Si per CHA cage values approximating to 1 are normally obtained.
• templates of formula I it is possible to achieve Si per CHA cage ratios as low as 0.
• the preferred template in this context is N,N-dimethylcyclohexylamine, providing Si per CHA cage ratios of less than 0.98.
• the sources of aluminum, phosphorus and silicon suitable for use in the synthesis of molecular sieves according to the present invention are typically those known in the art or as described in the literature for the production of the SAPO concerned.
• the aluminum source may be, for example, an aluminum oxide (alumina), optionally hydrated, an aluminum salt, especially a phosphate, an aluminate, or a mixture thereof.
• a preferred source is a hydrated alumina, most preferably pseudoboehmite, which contains about 75% Al 2 O 3 and 25% H 2 O by weight.
• the source of phosphorus is a phosphoric acid, especially orthophosphoric acid, but other sources, for example, organic phosphates, e.g., triethyl phosphate, and aluminophosphates may be used.
• the source of silicon is silica, for example colloidal silica, fumed silica, or an organic silicon source, e.g., a tetraalkyl orthosilicate, especially tetraethyl orthosilicate. When tetraethylorthosilicate is used as a source of silicon, CHA/AEI intergrowth of very high CHA character is obtained.
• the molecular sieve synthesis mixture may also contain a source of fluoride ions.
• the source of fluoride ions may be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture.
• Non-limiting examples of such sources of fluoride ions include salts containing one or several fluoride ions, such as metal fluorides, preferably, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, ammonium fluoride, tetraalkylammonium fluorides, such as tetramethylammonium fluoride, tetraethylammonium fluoride, hydrogen fluoride, [(C 2 H 5 ) 4 N] PF 6, NaHF 2 ⁇ HPF 6 NH 4 PF 6 , H 2 SiF 6 , (NH 4 ) 2 SiF 6 , NH 4 HF 2 , NaPF 6 , A1F 3 (anhydrous or hydrate
• the fluoride source is preferably selected from (NH 4 ) 2 SiF 6 , NH 4 HF 2 , HPF 6 , H 2 SiF 6 , A1F 3 (anhydrous or hydrate), NH 4 PF 6 , NaPF 6 , HF, more preferably (NH 4 ) 2 SiF 6 , HPF 6 , H 2 SiF 6 , A1F 3 (anhydrous or hydrate), NH 4 PF 6 , HF, and most preferably HF.
• the sihcoaluminophosphate molecular sieves of the present invention may be combined with one or more formulating agents, to form a molecular sieve catalyst composition or a formulated molecular sieve catalyst composition.
• the formulating agents may be one or more materials selected from the group consisting of binding agents, matrix or filler materials, catalytically active materials and mixtures thereof.
• This formulated molecular sieve catalyst composition is formed into useful shape and sized particles by well-known techniques such as spray drying, pelletizing, extrusion, and the like.
• binders that are useful in forming the molecular sieve catalyst composition.
• Non-limiting examples of binders that are useful alone or in combination include various types of hydrated alumina, silicas, and/or other inorganic oxide sol.
• One preferred alumina containing sol is aluminium chlorhydrol.
• the inorganic oxide sol acts like glue binding the synthesized molecular sieves and other materials such as the matrix together, particularly after thermal treatment. Upon heating, the inorganic oxide sol, preferably having a low viscosity, is converted into an inorganic oxide matrix component. For example, an alumina sol will convert to an aluminium oxide matrix following heat treatment.
• Aluminium chlorohydrol a hydroxylated aluminium based sol containing a chloride counter ion
• the binder is Al, 3 O 4 (OH) 24 Cl 7 » 12(H 2 O) as is described in G.M. Wolterman, et al., Stud. Surf. Sci. and Catal., 76, pages 105- 144 (1993), which is herein incorporated by reference.
• one or more binders are combined with one or more other non-limiting examples of alumina materials such as aluminium oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina, aluminium trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
• the binders are alumina sols, predominantly comprising aluminium oxide, optionally including some silicon.
• the binders are peptised alumina made by treating alumina hydrates such as pseudobohemite, with an acid, preferably an acid that does not contain a halogen, to prepare sols or aluminium ion solutions.
• the molecular sieve may be combined with one or more matrix material(s).
• Matrix materials are typically effective in reducing overall catalyst cost, act as thermal sinks assisting in shielding heat from the catalyst composition for example during regeneration, densifying the catalyst composition, increasing catalyst strength such as crush strength and attrition resistance, and to control the rate of conversion in a particular process.
• Non-limiting examples of matrix materials include one or more of the following: rare earth metals, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof, for example silica- magnesia, silica-zirconia, silica-titania, silica-alumina and silica-alumina-thoria.
• matrix materials are natural clays such as those from the families of montmorillonite and kaolin. These natural clays include sabbentonites and those kaolins known as, for example, Dixie, McNamee, Georgia and Florida clays.
• Non-limiting examples of other matrix materials include: haloysite, kaolinite, dickite, nacrite, or anauxite.
• the matrix material preferably any of the clays, are subjected to well known modification processes such as calcination and/or acid treatment and/or chemical treatment.
• a binder Upon combining the molecular sieve and the matrix material, optionally with a binder, in a liquid to form a slurry, mixing, preferably rigorous mixing is needed to produce a substantially homogeneous mixture containing the molecular sieve.
• suitable liquids include one or a combination of water, alcohol, ketones, aldehydes, and/or esters. The most preferred liquid is water.
• the slurry is colloid-milled for a period of time sufficient to produce the desired slurry texture, sub-particle size, and/or sub-particle size distribution.
• the molecular sieve and matrix material, and the optional binder may be in the same or different liquid, and may be combined in any order, together, simultaneously, sequentially, or a combination thereof. In the preferred embodiment, the same liquid, preferably water is used.
• the slurry of the molecular sieve, binder and matrix materials is mixed or milled to achieve a sufficiently uniform slurry of sub- particles of the molecular sieve catalyst composition that is then fed to a forming unit that produces the molecular sieve catalyst composition.
• the forming unit is spray dryer. Typically, the forming unit is maintained at a temperature sufficient to remove most of the liquid from the slurry, and from the resulting molecular sieve catalyst composition.
• the resulting catalyst composition when formed in this way takes the form of microspheres.
• the formulated molecular sieve catalyst composition contains from about 1% to about 99%, more preferably from about 5% to about 90%, and most preferably from about 10% to about 80%, by weight of the molecular sieve based on the total weight of the molecular sieve catalyst composition.
• the weight percent of binder in or on the spray dried molecular sieve catalyst composition based on the total weight of the binder, molecular sieve, and matrix material is from about 2% by weight to about 30%) by weight, preferably from about 5% by weight to about 20% by weight, and more preferably from about 7% by weight to about 15% by weight.
• a heat treatment such as calcination, at an elevated temperature is usually performed.
• a conventional calcination environment is air that typically includes a small amount of water vapour.
• Typical calcination temperatures are in the range from about 400°C to about 1,000°C, preferably from about 500°C to about 800°C, and most preferably from about 550°C to about 700°C, preferably in a calcination environment such as air, nitrogen, helium, flue gas (combustion product lean in oxygen), or any combination thereof.
• calcination of the formulated molecular sieve catalyst composition is carried out in any number of well known devices including rotary calciners, fluid bed calciners, batch ovens, and the like. Calcination time is typically dependent on the degree of hardening of the molecular sieve catalyst composition and the temperature.
• the catalyst compositions of the present invention may comprise one or several other catalytically active materials, such as silicoaluminophosphates or aluminophosphates having a different framework type than the molecular sieves of the present invention or zeolites (aluminosilicates) of any framework type.
• the molecular sieve of the present invention may be bound to another molecular sieve, as disclosed for example in the following: SAPO-34 bound AlPO 4 -5 (U.S. Patent No. 5,972,203), PCT WO 98/57743 published December 23, 1988 (molecular sieve and Fischer-Tropsch), U.S. Patent No.
• the molecular sieve of the present invention may be combined with a metal catalyst, for example as a Fischer-Tropsch catalyst.
• the molecular sieve catalysts and compositions of the present invention are useful in a variety of processes including: cracking, hydrocracking, isomerization, polymerisation, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, absorption, alkylation, transalkylation, dealkylation, hydrodecylization, disproportionation, oligomerization, dehydrocyclization and combinations thereof.
• the preferred processes of the present invention include a process directed to the conversion of a feedstock comprising one or more oxygenates to one or more olefin(s) and a process directed to the conversion of ammonia and one or more oxygenates to alkyl amines and in particular methylamines.
• the feedstock contains one or more oxygenates, more specifically, one or more organic compound(s) containing at least one oxygen atom.
• the oxygenate in the feedstock is one or more alcohol(s), preferably aliphatic alcohol(s) where the aliphatic moiety of the alcohol(s) has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.
• the alcohols useful as feedstock in the process of the invention include lower straight and branched chain aliphatic alcohols and their unsaturated counterparts.
• Non-limiting examples of oxygenates include methanol, ethanol, n- propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, di- isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid, and mixtures thereof.
• GTO methanol-to-olefins
• MTO methanol-to-olefins
• the feedstock in one embodiment, contains one or more diluent(s), typically used to reduce the concentration of the feedstock, and generally non- reactive to the feedstock or molecular sieve catalyst composition.
• diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane, and propane), essentially non-reactive aromatic compounds, and mixtures thereof.
• the most preferred diluents are water and nitrogen, with water being particularly preferred.
• the process for converting a feedstock, especially a feedstock containing one or more oxygenates, in the presence of a molecular sieve catalyst composition of the invention is carried out in a reaction process in a reactor, where the process is a fixed bed process, a fluidised bed process (includes a turbulent bed process), preferably a continuous fluidised bed process, and most preferably a continuous high velocity fluidised bed process.
• a fluidised bed process includes a turbulent bed process
• the reaction processes can take place in a variety of catalytic reactors such as hybrid reactors that have a dense bed or fixed bed reaction zones and/or fast fluidised bed reaction zones coupled together, circulating fluidised bed reactors, riser reactors, and the like. Suitable conventional reactor types are described in for example U.S. Patent No.
• the preferred reactor type are riser reactors generally described in
• a fluidised bed process or high velocity fluidised bed process includes a reactor system, a regeneration system and a recovery system.
• the reactor system preferably is a fluid bed reactor system having a first reaction zone within one or more riser reactor(s) and a second reaction zone within at least one disengaging vessel, preferably comprising one or more cyclones.
• the one or more riser reactor(s) and disengaging vessel is contained within a single reactor vessel.
• Fresh feedstock preferably containing one or more oxygenates, optionally with one or more diluent(s) is fed to the one or more riser reactor(s) in which a molecular sieve catalyst composition or coked version thereof is introduced.
• the molecular sieve catalyst composition or coked version thereof is contacted with a liquid or gas, or combination thereof, prior to being introduced to the riser reactor(s), preferably the liquid is water or methanol, and the gas is an inert gas such as nitrogen.
• the feedstock entering the reactor system is preferably converted, partially or fully, in the first reactor zone into a gaseous effluent that enters the disengaging vessel along with a coked molecular sieve catalyst composition.
• cyclone(s) within the disengaging vessel are designed to separate the molecular sieve catalyst composition, preferably a coked molecular sieve catalyst composition, from the gaseous effluent containing one or more olefin(s) within the disengaging zone. Cyclones are preferred, however, gravity effects within the disengaging vessel will also separate the catalyst compositions from the gaseous effluent. Other methods for separating the catalyst compositions from the gaseous effluent include the use of plates, caps, elbows, and the like. [0082] In one embodiment of the disengaging system, the disengaging system includes a disengaging vessel; typically a lower portion of the disengaging vessel is a stripping zone.
• the coked molecular sieve catalyst composition is contacted with a gas, preferably one or a combination of steam, methane, carbon dioxide, carbon monoxide, hydrogen, or an inert gas such as argon, preferably steam, to recover adsorbed hydrocarbons from the coked molecular sieve catalyst composition that is then introduced to the regeneration system.
• a gas preferably one or a combination of steam, methane, carbon dioxide, carbon monoxide, hydrogen, or an inert gas such as argon, preferably steam
• the stripping zone is in a separate vessel from the disengaging vessel and the gas is passed at a gas hourly superficial velocity (GHSN) of from 1 hr "1 to about 20,000 hr "1 based on the volume of gas to volume of coked molecular sieve catalyst composition, preferably at an elevated temperature from 250°C to about 750°C, preferably from about 350°C to 650°C, over the coked molecular sieve catalyst composition.
• GHSN gas hourly superficial velocity
• the conversion temperature employed in the conversion process, specifically within the reactor system, is in the range of from about 200°C to about 1000°C, preferably from about 250°C to about 800°C, more preferably from about 250°C to about 750 °C, yet more preferably from about 300°C to about 650°C, yet even more preferably from about 350°C to about 600°C most preferably from about 350°C to about 550°C.
• the conversion pressure employed in the conversion process varies over a wide range including autogenous pressure.
• the conversion pressure is based on the partial pressure of the feedstock exclusive of any diluent therein.
• the conversion pressure employed in the process is in the range of from about 0.1 kPaa to about 5 MPaa, preferably from about 5 kPaa to about 1 MPaa, and most preferably from about 20 kPaa to about 500 kPaa.
• the weight hourly space velocity (WHSN), particularly in a process for converting a feedstock containing one or more oxygenates in the presence of a molecular sieve catalyst composition within a reaction zone, is defined as the total weight of the feedstock excluding any diluents to the reaction zone per hour per weight of molecular sieve in the molecular sieve catalyst composition in the reaction zone.
• the WHSN is maintained at a level sufficient to keep the catalyst composition in a fluidised state within a reactor.
• the WHSN ranges from about 1 hr " ' to about 5000 hr " ⁇ preferably from about 2 hr “1 to about 3000 hr “1 , more preferably from about 5 hr “1 to about 1500 hr “1 , and most preferably from about 10 hr '1 to about 1000 hr “1 .
• the WHSN is greater than 20 hr "1 ; preferably the WHSV for conversion of a feedstock containing methanol and dimethyl ether is in the range of from about 20 hr "! to about 300 hr "1 .
• the superficial gas velocity (SGN) of the feedstock including diluent and reaction products within the reactor system is preferably sufficient to fluidise the molecular sieve catalyst composition within a reaction zone in the reactor.
• the SGV in the process, particularly within the reactor system, more particularly within the riser reactor(s), is at least 0.1 meter per second (m/s), preferably greater than 0.5 m s, more preferably greater than 1 m/s, even more preferably greater than 2 m s, yet even more preferably greater than 3 m/s, and most preferably greater than 4 m/s. See for example U.S. Patent Application Serial No. 09/708,753 filed November 8, 2000, which is herein incorporated by reference.
• the process is operated at a WHSV of at least 20 hr "1 and a Temperature Corrected Normalized Methane Selectivity (TCNMS) of less than 0.016, preferably less than or equal to 0.01. See for example U.S. Patent No. 5,952,538, which is herein fully incorporated by reference.
• TNMS Temperature Corrected Normalized Methane Selectivity
• the coked molecular sieve catalyst composition is withdrawn from the disengaging vessel, preferably by one or more cyclones(s), and introduced to the regeneration system.
• the regeneration system comprises a regenerator where the coked catalyst composition is contacted with a regeneration medium, preferably a gas containing oxygen, under general regeneration conditions of temperature, pressure and residence time.
• Non-limiting examples of the regeneration medium include one or more of oxygen, O 3 , SO 3 , N 2 O, NO, NO 2 , N 2 O 5 , air, air diluted with nitrogen or carbon dioxide, oxygen and water (U.S. Patent No. 6,245,703), carbon monoxide and/or hydrogen.
• the regeneration conditions are those capable of burning coke from the coked catalyst composition, preferably to a level less than 0.5 weight percent based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system.
• the coked molecular sieve catalyst composition withdrawn from the regenerator forms a regenerated molecular sieve catalyst composition.
• the regeneration temperature is in the range of from about 200°C to about 1500°C, preferably from about 300°C to about 1000°C, more preferably from about 450°C to about 750°C, and most preferably from about 550°C to 700°C.
• the regeneration pressure is in the range of from about 15 psia (103 kPaa) to about 500 psia (3448 kPaa), preferably from about 20 psia (138 kPaa) to about 250 psia (1724 kPaa), more preferably from about 25 psia (172kPaa) to about 150 psia (1034 kPaa), and most preferably from about 30 psia (207 kPaa) to about 60 psia (414 kPaa).
• the preferred residence time of the molecular sieve catalyst composition in the regenerator is in the range of from about one minute to several hours, most preferably about one minute to 100 minutes, and the preferred volume of oxygen in the gas is in the range of from about 0.01 mole percent to about 5 mole percent based on the total volume of the gas.
• regeneration promoters typically metal containing compounds such as platinum, palladium and the like, are added to the regenerator directly, or indirectly, for example with the coked catalyst composition.
• a fresh molecular sieve catalyst composition is added to the regenerator containing a regeneration medium of oxygen and water as described in U.S. Patent No. 6,245,703, which is herein fully incorporated by reference.
• a portion of the coked molecular sieve catalyst composition from the regenerator is returned directly to the one or more riser reactor(s), or indirectly, by pre-contacting with the feedstock, or contacting with fresh molecular sieve catalyst composition, or contacting with a regenerated molecular sieve catalyst composition or a cooled regenerated molecular sieve catalyst composition.
• Coke levels on the molecular sieve catalyst composition are measured by withdrawing from the conversion process the molecular sieve catalyst composition at a point in the process and determining its carbon content.
• Typical levels of coke on the molecular sieve catalyst composition, after regeneration is in the range of from 0.01 weight percent to about 15 weight percent, preferably from about 0.1 weight percent to about 10 weight percent, more preferably from about 0.2 weight percent to about 5 weight percent, and most preferably from about 0.3 weight percent to about 2 weight percent based on the total weight of the molecular sieve and not the total weight of the molecular sieve catalyst composition.
• the mixture of fresh molecular sieve catalyst composition and regenerated molecular sieve catalyst composition and/or cooled regenerated molecular sieve catalyst composition contains in the range of from about 1 to 50 weight percent, preferably from about 2 to 30 weight percent, more preferably from about 2 to about 20 weight percent, and most preferably from about 2 to about 10 coke or carbonaceous deposit based on the total weight of the mixture of molecular sieve catalyst compositions. See for example U.S. Patent No. 6,023,005, which is herein fully incorporated by reference.
• the gaseous effluent is withdrawn from the disengaging system and is passed through a recovery system.
• Recovery systems generally comprise one or more or a combination of a various separation, fractionation and/or distillation towers, columns, splitters, or trains, reaction systems such as ethylbenzene manufacture (U.S. Patent No. 5,476,978) and other derivative processes such as aldehydes, ketones and ester manufacture (U.S. Patent No. 5,675,041), and other associated equipment for example various condensers, heat exchangers, refrigeration systems or chill trains, compressors, knock-out drums or pots, pumps, and the like.
• the molecular sieve materials and catalyst compositions of the present invention may be used in the manufacture of alkylamines, using ammonia. Examples of suitable processes are as described in published European Patent Application EP 0 993 867 Al, and in U.S. Patent No. 6, 153, 798 to Hidaka et.al, which are herein fully incorporated by reference.
• the molecular sieve preparation mixtures for which x 0.2 or 0.3 gave pure sihcoaluminophosphate molecular sieves having the CHA framework type.
• the product yields (expressed as the weight percent of the final product versus the weight of the starting gel) along with the chemical compositions of the products as determined by elemental analysis, are given in Table II.

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