CN1659102A - Synthesis of aluminophosphates and silicoaluminophosphates - Google Patents

Synthesis of aluminophosphates and silicoaluminophosphates Download PDF

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CN1659102A
CN1659102A CN038134950A CN03813495A CN1659102A CN 1659102 A CN1659102 A CN 1659102A CN 038134950 A CN038134950 A CN 038134950A CN 03813495 A CN03813495 A CN 03813495A CN 1659102 A CN1659102 A CN 1659102A
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molecular sieve
template
framework types
catalyst composition
arbitrary
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CN1302989C (en
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曹光
M·J·谢
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ExxonMobil Chemical Patents Inc
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    • 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)
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    • 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
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    • 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
    • B01J35/40—
    • 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

Abstract

The invention is directed to a method of synthesising silicoaluminophosphate and aluminophosphate molecular sieves using synthesis templates that contain at least one template of general formula (I) R<1>R<2>N-R<3> (I) wherein - R<1> and R<2> 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; - R<3> 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. In particular, the present invention relates to the synthesis of silicoaluminophosphate molecular sieves of the CHA framework tgammape having a low silicon to aluminium atomic ratio.

Description

Synthesizing of aluminum phosphate and silicon aluminium phosphate
Invention field
The present invention relates to the silicon aluminium phosphate of CHA framework types and synthesizing of aluminium phosphate molecular sieve.Particularly, the present invention relates to silicoaluminophosphamolecular molecular sieves synthetic of the CHA framework types of low silicon/al atomic ratio.
Background of invention
Produce alkene by petroleum by catalysis or steam cracking method traditionally.These cracking processes especially steam cracking are produced light olefin such as ethene and/or propylene by various hydrocarbon raw materials.Known oxygenatedchemicals especially alcohol can change into light olefin for some time as methyl alcohol.Preferred methanol conversion method is commonly referred to as the methanol-to-olefins conversion method, wherein makes methanol conversion become ethene and propylene in the presence of molecular sieve.
Be best suited for that to make methanol conversion become some molecular sieves of alkene be metal aluminophosphates such as silicon aluminium phosphate (SAPO ' s).Many kinds of SAPO molecular sieves known in the art, wherein the example of outbalance comprises SAPO-5, SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-41 and SAPO-56.To the conversion of olefines process, the SAPO molecular sieve that the CHA skeleton arranged especially SAPO-34 is the catalyzer of particularly important for methyl alcohol.The CHA framework types has ABC to pile up two six-membered ring structures of arrangement.The pore opening of this structure is limited by octatomic ring, and diameter is about 4.0 dusts, the cylindrical cage in this structure be about 10 * 6.7 dusts (" Atlas of Zeolite Framework Types ", 2001,5th Edition, p.96).Other SAPO molecular sieve of CHA framework types comprises SAPO-44, SAPO-47 and ZYT-6.
The synthetic of SAPO molecular sieve is very complicated process.Many variablees of control that need are arranged to optimize described synthesizing aspect purity, output and the quality of produced SAPO molecular sieve.The variable of particularly important is the selection of synthetic template, and it is the framework types of the synthetic gained SAPO of decision usually.US4310 440 (Wilson etc.) instruction " template that is applicable to some material of preparation is not all substances that all are applicable to this genus class of preparation ".It also is known that same template can cause forming different framework types.
Among the US4 440 871 (Lok etc.), SAPO material synthetic of many different framework types is described with some specific exampless.Also disclose many possible organic formwork agents, some specific exampless have been arranged.The material of number of C HA framework types has been described in the described specific examples.Report prepares SAPO-34 with the mixture of tetraethylammonium hydroxide (TEAOH) or Isopropylamine or TEAOH and dipropyl amine (DPA) as template.The specific embodiment that uses hexahydroaniline in preparation SAPO-44 is also disclosed in this patent.Though also described other mould material in this patent, do not pointed out to be applicable to other template of the SAPO ' s for preparing the CHA framework types.
In US4 440 871, reported the synthetic of SAPO-34, separately or with tetraethylammonium hydroxide (TEAOH) that Diisopropylamine (DPA) is used in combination be the preferred template agent that is used to prepare SAPO-34 always.But use TEAOH and DPA also to have problems.When using separately, TEAOH makes the range limited of synthetic parameters.For example, TEAOH also is the template of the SAPO-18 of synthetic AEI framework types under certain conditions.Therefore TEAOH relatively can't stand the variation of synthesis condition.Sometimes make TEAOH and DPA combination.But the boiling point of DPA lower (110 ℃), thereby need to deal with the highly compressed production unit.In some country, use DPA to need the approval of concrete management office, because of its toxicity.And DPA is a kind of aggressiveness template, usually and being dissolved with again of molecular sieve described in the silicoaluminophosphamolecular molecular sieves building-up process involve, thereby cause the second-rate of crystalline product because of the crystalline surface pitting.Final certification is difficult to prepare the pure phase CHA silicoaluminophosphamolecular molecular sieves of low silicon/al atomic ratio so far.
Report is made the SAPO-44 that template obtains " as principal phase " with hexahydroaniline among the US4 440 871.
Among the US6 162 415 (Liu etc.) with identical template but under the situation of the ratio in control template agent and aluminium source and phosphorus source and the ratio in aluminium source the purer CHA SAPO-44 of acquisition.
Report uses methylbutylamine to produce SAPO-47 among the EP0 993 867, uses hexahydroaniline to produce impure SAPO-44.The boiling point of methylbutylamine even also lower than DPA is 91 ℃.
Report utilizes N among the embodiment 102 of US4 861 739 (Pellet etc.), and the N-diethylethanolamine is produced CoAPSO-47, Si concentrate on crystal periphery and Co at the center.
Among the US4 310 440 (Wilson etc.), trolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N methyldiethanol amine and N-Mono Methyl Ethanol Amine all are used to prepare AlPO 4-5 (aluminum phosphates of AFI framework types).Also report the AlPO that the N-Mono Methyl Ethanol Amine produces the AWO framework types 4-21.
The report diethanolamine produces SAPO-34 and SAPO-5 among the EP0 993 867 under different synthesis conditions.
For improving AlPO 4Or the SAPO molecular sieve is synthetic, and this area has been done many trials.A kind of approach is to add fluoride sources in synthetic mixture.
Among the US5 096 684 (Guth etc.), find that morpholine and tetraethylammonium hydroxide are the template of production SAPO-34 in the presence of HF.According to titles such as Guth, HF and organic formwork agent are used in combination the silicon aluminium phosphate that produces heat and hydrolysis-stable property improvement.
Among the US4 786 487 (Kuehl etc.), by comprising tetramethylammonium hydroxide and producing SAPO-20 from the synthetic mixture of the fluorion of the fluorochemical of soluble fluoride source such as Na, K and ammonium.
Among the US6 001 328 (Lillerud etc.), be expressed as the silicon aluminium phosphate of UiO-S7 with five hydronium(ion) oxidation tetramethylammoniums or tetramethylammonium hydroxide and HF combined preparation.
Ph.D. report hangs down silicon SAPO-34 (being expressed as UiO-S4) with TEAOH template and HF combinations produce in the paper (E.H.Halvorsen, University of Oslo, 1996).
Reports such as Wilson for methyl alcohol lower Si content to conversion of olefines reaction be useful (Microporous and Mesoporous Materials, 29, 117-126,1999).The low effect that reduction propane growing amount is arranged and reduce catalyst deactivation of Si content.
As seen, it is a lot of that utilization can select to be used for the trial of synthetic template of CHA framework types from open source literature described herein, success limited.Thereby wish to find the silicon aluminium phosphate that is exclusively used in synthetic CHA framework types or the new synthetic template of aluminium phosphate molecular sieve.Another purpose is to find the final composition of the silicon aluminium phosphate that can more effectively control the CHA framework types particularly to control the new template system of Si/Al (silicon/aluminium atom) ratio of the finished product.In the molecular sieve of CHA framework types, the Si/Al atomic ratio is typically expressed as the Siliciumatom number of each CHA cage of described molecular sieve, and each CHA cage is formed (the T atom is Si, Al or P) by 12 T atoms.Another purpose is to find the silicon aluminium phosphate that is applicable in the wide region of molecular sieve synthesis condition synthetic CHA framework types or the template of aluminium phosphate molecular sieve again.
Summary of the invention
The invention provides a kind of preparation method of crystalline molecular sieve of CHA framework types, described method comprises:
A) provide the synthetic mixture of the organic formwork agent that comprises aluminium source, phosphorus source, silicon source and at least a formula (I)
R 1R 2N-R 3????(I)
Wherein
-R 1And R 2Be independently selected from the alkyl and the hydroxyalkyl that 1 to 3 carbon atom is arranged of 1 to 3 carbon atom;
-R 3Be selected from alternatively 4-to the 8-unit cycloalkyl that replaced by 1 to 3 alkyl that 1 to 3 carbon atom arranged, 1 to 3 heteroatomic 4-to 8-unit heterocyclic radical is arranged, described heterocyclic radical is had the alkyl of 1 to 3 carbon atom to replace by 1 to 3 alternatively, and the heteroatoms in the described heterocyclic radical is selected from O, N and S; With
B) make crystalline molecular sieve crystallization from described reaction mixture of CHA framework types.
The organic formwork agent of preferred formula (I) is the template of formula (II)
(CH 3) 2N-R 3????(II)
R wherein 3For alternatively by 1 to 3 methyl substituted 4-to 8-unit cycloalkyl.
More preferably described organic formwork agent is selected from N, N-dimethyl-hexahydroaniline, N, N-dimethyl-methyl cyclohexylamine, N, N-dimethyl-cyclopentamine, N, N-dimethyl-methyl cyclopentamine, N, N-dimethyl-cycloheptylamine, N, N-dimethyl-methyl cycloheptylamine.Most preferably described organic formwork agent is N, N-dimethyl-hexahydroaniline.
The inventive method produces the molecular sieve that the CHA framework types of unique x-ray diffraction pattern is arranged when just synthesizing.
In the one embodiment of this invention, a kind of silicoaluminophosphamolecular molecular sieves is provided, basically be the CHA framework types, comprise the template of template, the preferred formula II of at least a formula I, more preferably N in its intracrystalline (intra-crystalline) structure, N-dimethyl-hexahydroaniline.
In another embodiment, the invention provides a kind of crystallization silicoaluminophosphamolecular molecular sieves of the framework types of CHA basically, its characteristic X-ray powder diagram comprises d-spacing shown in the Table I a at least:
Table I a
??2θ ??d(A) ????I％
??9.46 ??9.34 ????63
??12.86 ??6.88 ????12
??13.98 ??6.33 ????16
??16.02 ??5.53 ????51
??17.80 ??4.98 ????24
??20.62 ??4.30 ????100
??22.42 ??3.96 ????11
??25.02 ??3.56 ????36
??25.96 ??3.43 ????16
??30.68 ??2.91 ????37
??31.18 ??2.87 ????18
Preferably the invention provides a kind of crystallization silicoaluminophosphamolecular molecular sieves of the framework types of CHA basically, its characteristic X-ray powder diagram comprises d-spacing shown in the Table I b at least:
Table I b
??2θ ??d(A) ????I％
??9.46 ??9.34 ????63
??12.86 ??6.88 ????12
??13.98 ??6.33 ????16
??16.02 ??5.53 ????51
??17.80 ??4.98 ????24
??19.06 ??4.65 ????2
??20.62 ??4.30 ????100
??22.06 ??4.03 ????8
??22.42 ??3.96 ????11
??23.10 ??3.85 ????7
??25.02 ??3.56 ????36
??25.96 ??3.43 ????16
??27.72 ??3.22 ????4
??28.26 ??3.16 ????4
??29.62 ??3.01 ????4
??30.68 ??2.91 ????37
??31.18 ??2.87 ????18
??31.68 ??2.82 ????2
??32.44 ??2.76 ????2
??33.62 ??2.66 ????3
??34.60 ??2.59 ????8
??35.02 ??2.56 ????1
??36.18 ??2.48 ????5
??38.76 ??2.32 ????1
??39.84 ??2.26 ????3
??42.98 ??2.10 ????3
??43.58 ??2.08 ????3
??45.28 ??2.00 ????1
??46.92 ??1.93 ????1
??47.84 ??1.90 ????4
??49.02 ??1.86 ????4
??49.52 ??1.84 ????1
The preferred described molecular sieve that the x-ray diffraction pattern of Table I a or Ib arranged is included in the N in its intracrystalline structure, N-dimethylcyclohexylamine.
In another embodiment, the invention provides a kind of crystallization silicoaluminophosphamolecular molecular sieves of the framework types of CHA basically, its characteristic X-ray powder diagram comprises d-spacing shown in the Table III a at least:
Table III a
????2θ ????d(A) ????I％
????9.54 ????9.26 ????100
????14.04 ????6.30 ????20
????15.68 ????5.64 ????15
????16.08 ????5.51 ????57
????17.88 ????4.96 ????25
????18.00 ????4.92 ????27
????20.68 ????4.29 ????76
????21.22 ????4.18 ????21
????25.04 ????3.55 ????32
????25.44 ????3.50 ????20
????26.00 ????3.42 ????10
????30.74 ????2.91 ????22
????31.04 ????2.88 ????26
????31.18 ????2.87 ????19
Preferably the invention provides a kind of crystallization silicoaluminophosphamolecular molecular sieves of the framework types of CHA basically, its characteristic X-ray powder diagram comprises d-spacing shown in the Table III b at least:
Table III b
????2θ ????d(A) ????I％
????9.54 ????9.26 ????100
????12.92 ????6.85 ????9
????13.36 ????6.62 ????4
????14.04 ????6.30 ????20
????14.56 ????6.08 ????3
????15.68 ????5.64 ????15
????16.08 ????5.51 ????57
????16.80 ????5.27 ????8
????17.88 ????4.96 ????25
????18.00 ????4.92 ????27
????20.68 ????4.29 ????76
????21.22 ????4.18 ????21
????22.12 ????4.02 ????7
????22.60 ????3.93 ????8
????23.18 ????3.83 ????4
????25.04 ????3.55 ????32
????25.44 ????3.50 ????20
????26.00 ????3.42 ????10
????26.26 ????3.39 ????3
????27.00 ????3.30 ????3
????28.28 ????3.15 ????4
????30.36 ????2.94 ????9
????30.74 ????2.91 ????22
????31.04 ????2.88 ????26
????31.18 ????2.87 ????19
????31.60 ????2.83 ????9
????33.64 ????2.66 ????3
????34.60 ????2.59 ????5
????36.24 ????2.48 ????5
????43.02 ????2.10 ????4
The preferred described molecular sieve that the x-ray diffraction pattern of Table III a or IIIb arranged is included in the N in its intracrystalline structure, N-dimethylcyclohexylamine and fluorochemical (more preferably hydrogen fluoride).
In another embodiment, the invention provides a kind of production method of molecular sieve catalyst composition, described method comprises that forming the mixture that comprises at least a molecular sieve of the present invention and at least a preparaton forms molecular sieve catalyst composition.
In another embodiment, the invention provides a kind of molecular sieve catalyst composition again, comprise and at least a molecular sieve of the present invention of at least a preparaton blended.
Again in another embodiment, the invention provides the template of template, the preferred formula II of formula I, more preferably N, the N-dimethylcyclohexylamine is used for the purposes of the silicon aluminium phosphate of synthetic CHA framework types alternatively in the presence of fluoride source.
In another embodiment, the invention provides a kind of production method of molecular sieve catalyst composition, described method comprises and forms the template comprise the template that comprises at least a formula I at least a its intracrystalline structure, preferred formula II, more preferably N, N-dimethylcyclohexylamine or utilize the template of template, the preferred formula II of formula I, more preferably N, the molecular sieve that the method for N-dimethylcyclohexylamine obtains and the mixture of at least a preparaton form molecular sieve catalyst composition.
Again in another embodiment, the invention provides a kind of molecular sieve catalyst composition, comprise with its intracrystalline structure of at least a preparaton blended in comprise the template of template, the preferred formula II of at least a formula I, more preferably N, N-dimethylcyclohexylamine or utilize the template of template, the preferred formula II of formula I, more preferably N, at least a silicoaluminophosphamolecular molecular sieves that the method for N-dimethylcyclohexylamine obtains.
The present invention or the molecular sieve for preparing by the inventive method are to be applicable to make raw material preferably contain the catalyzer that the oxygen feedstock conversion becomes one or more alkene.
The accompanying drawing summary
Fig. 1 illustrates in its intracrystalline structure that crystallization obtains after 3 days and comprises N, the XRD figure of the crystalline molecular sieve of the CHA framework types of N-dimethylcyclohexylamine, the silicon sources of using different amounts in the described molecular sieve synthetic mixture.
Fig. 2 illustrates in its intracrystalline structure that crystallization obtains after 7 days and comprises N, the XRD figure of the crystalline molecular sieve of the CHA framework types of N-dimethylcyclohexylamine, the silicon sources of using different amounts in the described molecular sieve synthetic mixture.
Fig. 3 illustrates in its intracrystalline structure that crystallization obtains after 3 days and comprises N, the XRD figure of the crystalline molecular sieve of the CHA framework types of N-dimethylcyclohexylamine, the silicon source of using HF and different amounts in the described molecular sieve synthetic mixture.
Detailed Description Of The Invention
Preface
The present invention relates generally to a kind of crystalline aluminophosphate of basically CHA framework types and the synthetic method of SAPO. Especially, found that one group of special organic amine is the aluminum phosphate of synthetic CHA framework types and effective template of silicoaluminophosphamolecular molecular sieves. Found that the N-dimethyl cyclohexyl amine prepares the SAPO molecular sieve, then obtains the quite high SAPOs of purity of CHA framework types if with the template of the template of formula as described below (I), preferred formula (II), N most preferably. In addition, in another embodiment, can utilize the i.e. SAPOs of the CHA framework types of low acidity of the synthetic low Si/Al atomic ratio of these templates.
Molecular sieve
Molecular sieve of the present invention can represent with following empirical formula (butt):
                mR：(Si xAl yP z)O 2
Wherein R represents the template of at least a formula (I)
                R 1R 2N-R 3    (I)
Wherein
R 1Be selected from alkyl or hydroxyalkyl;
R 2Be selected from alkyl or hydroxyalkyl;
R 3Be selected from alternatively the cycloalkyl that 4 to 8 carbon atoms are arranged that replaced by 1 to 3 alkyl, 1 to 3 heteroatomic 4-to 8-unit heterocyclic radical is arranged, described heterocyclic radical is replaced by 1 to 3 alkyl alternatively, and the hetero atom in the described heterocyclic radical is selected from O, N and S,
All alkyl and alkoxyl have 1 to 3 carbon atom independently; M is the molal quantity/mole (Si of RxAl yP z)O 2, the value of m is 0.0417 to 0.3333, preferred 0.0624 to 0.166, most preferably 0.0667 to 0.1; X, y and z represent respectively the Si, the Al that exist with the tetrahedral oxide form and the molar fraction of P.
In one embodiment, m more than or equal to 0.04, x more than or equal to 0, y and z more than or equal to 0.01. In another embodiment, m is greater than 0.01 to about 0.3333 scope, and x is greater than 0 to about 0.31 scope, and y is in 0.25 to 1.0 scope, and z is in 0.25 to 0.9 scope; More preferably m is in 0.05 to 0.10 scope, and x is in 0.01 to 0.2 scope, most preferably 0.02 to 0.15, y in 0.4 to 0.9 scope, and z is in 0.3 to 0.9 scope. Alternatively, described molecular sieve can also comprise fluorine.
During with described molecular sieve roasting, described organic formwork agent is removed, gained aluminum phosphate or SAPO have the CHA framework types, and purity is quite high with regard to its framework types, almost do not have or do not have the commensal with other SAPO or aluminum phosphate framework types. When the CHA framework types basically of touching upon in this specification or purity is quite high with regard to its framework types SAPO, mean to comprise 60% or more CHA framework types, preferred 70% or more CHA framework types, more preferably 90% or more CHA framework types, most preferably 95% or the silicoaluminophosphamolecular molecular sieves of more CHA framework types by XRD determining.
Molecular sieve of the present invention can comprise a small amount of and commensal another kind of SAPO or aluminium phosphate molecular sieve. Described molecular sieve can comprise the coexisting phase of at least one AEI and CHA framework types. For example SAPO-18, AlPO4-18 and RUW-18 the AEI framework types is arranged. In another embodiment, described molecular sieve can comprise the mixture of commensal and non-commensal.
In one embodiment, the Si/Al of baked molecular sieve of the present invention than less than 0.167, preferably less than 0.134, be more preferably less than 0.100. In one preferred embodiment, the Si/Al of described molecular sieve than in 0 to 0.167 scope, more preferably in 0.02 to 0.167 scope even more preferably in 0.03 to 0.134 scope, most preferably in 0.03 to 0.100 scope.
Synthesizing of molecular sieve
General one or more hydrothermal crystallization synthesized silicon-aluminum phosphate and aluminium phosphate molecular sieve by aluminium source, phosphorus source, template and optional silicon source. Typically, in the methods of the invention, with aluminium source, phosphorus source, one or more template, optional silicon source and optionally the mixture of one or more metallic compound be placed in the pressure vessel (inert plastic such as teflon lined are arranged alternatively) of sealing, under the pressure and temperature of crystallization, heat until then the generation crystalline material reclaims by filtration, centrifugation and/or decantation.
During the typical case of silicoaluminophosphamolecular molecular sieves of the present invention is synthetic, make and contain phosphorus component, contain al composition and optional silicon containing component, preferably in the situation that stirs and/or stir and/or inoculate with crystalline material, mix alternatively forming synthetic mixture with alkali metal (in solvent such as water) and one or more template, then heating under crystallization pressure and the temperature conditions described in the US4 440 871 (all being incorporated herein for reference).
In the inventive method, the consumption of template makes template and aluminium oxide (Al in the reactant mixture2O 3) mol ratio in 0.6: 1.0 to 3.0: 1.0, preferred 1.0: 1.0 to 2.0: 1.0 scope.
Template used dose has general formula (I) in the inventive method
                R 1R 2N-R 3    (I)
Wherein
R 1Be selected from alkyl or hydroxyalkyl;
R 2Be selected from alkyl or hydroxyalkyl;
R 3Be selected from alternatively the cycloalkyl that 4 to 8 carbon atoms are arranged that replaced by 1 to 3 alkyl, 1 to 3 heteroatomic 4-to 8-unit heterocyclic radical is arranged, described heterocyclic radical is replaced by 1 to 3 alkyl alternatively, and the hetero atom in the described heterocyclic radical is selected from O, N and S,
All alkyl and alkoxyl have 1 to 3 carbon atom independently.
The organic formwork agent of preferred formula (I) is the template of formula (II)
                  (CH 3) 2N-R 3    (II)
Wherein
R 3Be selected from cycloalkyl, described cycloalkyl is alternatively by 1 to 3 methyl substituted, and described cycloalkyl has 4 to 8 carbon atoms, preferred 6 carbon atoms.
In the one preferred embodiment, the template of formula (I) or formula (II) is selected from wherein R 3Be selected from the template of the formula I or the formula II of cyclohexyl, methylcyclohexyl, Dimethylcyclohexyl, trimethylcyclohexyl, tetramethyl-ring hexyl, pentamethyl-cyclohexyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, trimethylammonium cyclopentyl, tetramethyl-ring amyl group, suberyl, methyl suberyl, dimethyl suberyl, trimethylammonium suberyl, tetramethyl-ring heptyl, pentamethyl-suberyl, hexamethyl suberyl and piperidyl.Most preferably described template is N, the N-dimethylcyclohexylamine.
In another (not preferred) embodiment, the added pattern agent that the template of formula (I) or formula (II) and one or more are usually used in producing the silicon aluminium phosphate of CHA framework types is used in combination.These added pattern agent comprise: tetraethyl ammonium compount such as tetraethylammonium hydroxide (TEAOH), phosphoric acid Tetrylammonium, fluoridize Tetrylammonium, tetraethyl-ammonium bromide, tetraethylammonium chloride and acetate Tetrylammonium, also comprise DPA, Isopropylamine, hexahydroaniline, morpholine, methylbutylamine, diethanolamine and triethylamine.
Typically, the preferred N of template of use formula (I) or formula (II), during the N-dimethylcyclohexylamine, the Si/CHA cage of the silicon aluminium phosphate of gained CHA framework types is than 0.1 to 1.0, in preferred 0.15 to 0.8, more preferably 0.2 to 0.7 the scope.With tetraethylammonium hydroxide during, obtain the silicon aluminium phosphate of Si/CHA cage ratio usually near 1 CHA framework types as unique organic formwork material.Typically, when using the template of formula I, can realize that the Si/CHA cage reaches 0 than low.Preferred in this regard template is N, and the N-dimethylcyclohexylamine provides to be lower than 0.98 Si/CHA cage ratio.
Aluminium, phosphorus and the silicon source by synthesis of molecular sieve of the present invention of being applicable to typically is known in the art or relates to those that describe in the document that SAPO produces.Described aluminium source can be for example aluminum oxide (hydration alternatively), aluminium salt (especially phosphoric acid salt), aluminate and composition thereof.Preferred aluminium source is hydrated aluminum oxide, pseudobochmite most preferably, comprises about 75%Al 2O 3And 25%H 2O (weight).Described phosphorus source is beneficial to and is phosphoric acid especially ortho-phosphoric acid, but also can use other source for example organophosphate such as triethyl phosphate and aluminophosphates.Described silicon source is beneficial to and is silicon oxide colloided silica, fumed silica or organosilicon source such as orthosilicic acid tetraalkyl ester tetraethyl orthosilicate especially for example.During as the silicon source, obtain the high CHA/AEI Symbiont of CHA feature with tetraethyl orthosilicate.
Described molecular sieve synthetic mixture can also comprise fluoride sources.Described fluoride sources can be can be in described molecular sieve synthetic mixture any compound of releasing fluoride ion.The limiting examples of this fluoride sources comprises and contains one or the salt such as the metal fluoride of several fluorions, preferred fluorinated sodium, Potassium monofluoride, Calcium Fluoride (Fluorspan), magnesium fluoride, strontium fluoride, barium fluoride, Neutral ammonium fluoride, fluoridize tetra-allkylammonium as fluoridize tetramethylammonium, fluoridize Tetrylammonium, hydrogen fluoride, [(C 2H 5) 4N] PF 6, NaHF 2, HPF 6NH 4PF 6, H 2SiF 6, (NH 4) 2SiF 6, NH 4HF 2, NaPF 6, AlF 3(anhydrous or hydrate), (NH 4) 3AlF 6, (NH 4) 2TiF 6, (NH 4) 2ZrF 6, (NH 4) 2GeF 6, (NH 4) 2SiF 6Described fluorine source is preferably selected from (NH 4) 2SiF 6, NH 4HF 2, HPF 6, H 2SiF 6, AlF 3(anhydrous or hydrate), NH 4PF 6, NaPF 6, HF, more preferably (NH 4) 2SiF 6, HPF 6, H 2SiF 6, AlF 3(anhydrous or hydrate), NH 4PF 6, HF, most preferably HF.
The preparation method of molecular sieve catalyst composition
Silicoaluminophosphamolecular molecular sieves of the present invention can be combined to form the molecular sieve catalyst composition of molecular sieve catalyst composition or preparation with one or more preparaton.Described preparaton can be one or more material that is selected from tackiness agent, matrix or packing material, catalytically active material and composition thereof.By known technology such as spraying drying, granulation and extruding etc. the molecular sieve catalyst composition of this preparation is made the particle that is fit to shape and size.
There are many different tackiness agents to be applicable to and form described molecular sieve catalyst composition.The limiting examples of the tackiness agent that is used alone or in combination comprises various types of hydrated aluminum oxides, silicon oxide and/or other inorganic oxide sol.A kind of preferred salic colloidal sol is aluminium chlorohydroxide colloidal sol (aluminium chlorhydrol).Described inorganic oxide sol is bonded together synthetic molecular sieve and other material such as matrix as glue, especially after thermal treatment.During heating, described inorganic oxide colloidal sol (preferably having low viscosity) changes into the inorganic oxide matrix component.For example thermal treatment rear oxidation aluminium colloidal sol will change into alumina substrate.
Aluminium chlorohydroxide colloidal sol (the aluminium base colloidal sol of hydroxylation that contains the chlorion that contends with) has following general formula: Al mO n(OH) oCl pX (H 2O), wherein m is 1 to 20, and n is 1 to 8, and o is 5 to 40, and p is 2 to 15, and x is 0 to 30.In one embodiment, described tackiness agent is Al 13O 4(OH) 24Cl 712 (H 2O), as G.M.Wolterman, et al., Stud.Surf.Sci.and Catal., 76, described in the p105-144 (1993), be incorporated herein for reference.In another embodiment, other limiting examples of one or more tackiness agent and one or more alumina material such as aluminum oxyhydroxide, gama-alumina, boehmite, diaspore and transitional alumina such as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, ε-aluminum oxide, κ-aluminum oxide and ρ-aluminum oxide, three aluminium hydroxides such as gibbsite, bayerite, promise gibbsite, doyelite, and composition thereof combination.
In another embodiment, described tackiness agent is an alumina sol, mainly comprises aluminum oxide, comprises some silicon alternatively.Again in another embodiment, described tackiness agent is to prepare the peptization aluminum oxide that colloidal sol or aluminum ion solution obtain with preferred not halogen-containing acid treatment hydrated aluminum oxide of acid such as pseudobochmite.
Described molecular sieve can make up with one or more body material.Body material can reduce the total cost of catalyzer usually, plays heat-absorbing action and helps to make catalyzer heat insulation for example at regeneration period, makes the catalyst composition densification, improves the conversion rate in catalyst strength such as shatter strength and wear resistance and the control special process.
The limiting examples of body material comprises following one or more: rare earth metal, metal oxide comprise titanium oxide, zirconium white, magnesium oxide, Thorotrast, beryllium oxide, quartz, silicon oxide or colloidal sol, and composition thereof, for example silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-titanium oxide, silica-alumina and silica-alumina-Thorotrast.In one embodiment, body material is the clay that natural clay if you would take off soil and kaolin group.These natural claies comprise sabbentonites and are called for example those kaolin of Dixie, McNamee, Georgia and Florida clay.The limiting examples of other body material comprises: haloysite, kaolinite, dickite, nakrite or anauxite.In one embodiment, make the preferred any clay of described body material through known modified technique such as roasting and/or acid treatment and/or chemical treatment.
When in liquid, making molecular sieve and body material form slurries with binder combination alternatively, need to mix (preferred violent the mixing) to produce the mixture that comprises described molecular sieve basically uniformly.The limiting examples of applicable liquid comprises one of water, alcohol, ketone, aldehyde and/or ester or combination.Most preferred liquid is water.In one embodiment, make described slurries colloidal state grind the sufficiently long time to produce desired slurries structure, sub-micro granularity and/or sub-micro size-grade distribution.
Described molecular sieve and body material and optionally tackiness agent can be in identical or different liquid can any orders, together, simultaneously, one after the other mix or its combination.In one preferred embodiment, use same liquid, preferably water.
In one embodiment, the slurries of described molecular sieve, tackiness agent and body material are mixed or grind obtaining enough the slurries of molecular sieve catalyst composition subparticle uniformly, infeed shaped device production molecular sieve catalyst composition then.In one preferred embodiment, described shaped device is a spray-dryer.Typically, shaped device being remained on is enough to remove under the temperature of most of liquid in described slurries and the gained molecular sieve catalyst composition.So the gained catalyst composition of moulding is a microspheroidal.
In another embodiment, the molecular sieve catalyst composition of being prepared comprises about 1 to about 99%, more preferably from about 5 to about 90%, most preferably from about 10 described molecular sieves to about 80% (weight), based on the gross weight of molecular sieve catalyst composition.
In another embodiment, based on the gross weight of tackiness agent, molecular sieve and body material, in the described spray-dired molecular sieve catalyst composition weight percent of tackiness agent be about 2 to about 30% (weight), preferred about 5 to about 20% (weight), more preferably from about 7 to about 15% (weight).
Form after the molecular sieve catalyst composition with drying or drying regime basically,, at high temperature heat-treat usually as roasting for further sclerosis and/or the activation of catalyst composition that makes generation.Roasting environment commonly used is an air, typically comprises a small amount of water vapor.Typical maturing temperature be about 400 to about 1000 ℃, preferred about 500 to about 800 ℃, most preferably from about 550 to about 700 ℃ scope, preferably in roasting environment such as air, nitrogen, helium, stack gas (combustion product lean in oxygen) or its any combination, carry out.
In one embodiment, the roasting of the molecular sieve catalyst composition of preparing comprises in rotary roasting furnace, fluidized-solids roaster and the batch furnace at any amount of well known device to be carried out.Roasting time depends on the hardenability and the temperature of molecular sieve catalyst composition usually.
Except that molecular sieve of the present invention, catalyst composition of the present invention can also comprise one or several other catalytically active material, as with the silicon aluminium phosphate of the different framework types of molecular sieve of the present invention or the zeolite (silico-aluminate) of aluminum phosphate or any framework types.In another embodiment, can make molecular sieve of the present invention and other molecular sieve for example US5 972 203 (SAPO-34 combines AlPO 4-5), disclosed molecular sieve and mesoporous molecular sieve (US6 284 696,5,098 684,5 102 643 and 5 108 725) are bonding among disclosed PCT WO98/57743 on December 23rd, 1988 (molecular sieve and Fischer-Tropsch), the US6 300535 (MFI-bound zeolite), all are incorporated herein for reference.May no longer need tackiness agent in this system.
In another embodiment, can make for example Fischer-Tropsch catalyst combination of molecular sieve of the present invention and metal catalyst.
The using method of described molecular sieve catalyst composition
Molecular sieve catalyst of the present invention and composition are applicable to many processes, comprising: cracking, hydrocracking, isomerization, polymerization, reformation, hydrogenation, dehydrogenation, dewaxing, Hydrodewaxing, absorption, alkylation, transalkylation, dealkylation, hydrogenated ring-opened, disproportionation, oligomeric, dehydrocyclization and combination thereof.
Preferable methods of the present invention comprises that relating to the method that makes the feedstock conversion that comprises one or more oxygenatedchemicals become one or more alkene makes the feedstock conversion that comprises one or more oxygenatedchemicals and ammonia become the particularly method of methylamine of alkylamine with relating to.
In the inventive method one preferred embodiment, described raw material comprises one or more oxygenatedchemicals, and more particularly one or more contains the organic compound of at least one Sauerstoffatom.In the most preferred embodiment of the inventive method, the oxygenatedchemicals in the described raw material is one or more alcohol, and preferably its moieties has 1 to 20 carbon atom, preferred 1 to 10 carbon atom, the fatty alcohol of 1 to 4 carbon atom most preferably.Be fit in the methods of the invention to comprise lower straight and branched aliphatic alcohol and unsaturated counterpart thereof as the alcohol of raw material.
The limiting examples of oxygenatedchemicals comprise methyl alcohol, ethanol, n-propyl alcohol, Virahol, methyl ethyl ether, dme, diethyl ether, diisopropyl ether, formaldehyde, methylcarbonate, Ketene dimethyl, acetate, and composition thereof.
Most preferred method be commonly referred to as gas to conversion of olefines (GTO) or methyl alcohol to conversion of olefines (MTO).In the MTO process, in the presence of molecular sieve catalyst composition, make the feedstock conversion that contains the oxygen raw material, most preferably contains methyl alcohol become one or more alkene, preferably be mainly ethene and/or propylene (being commonly referred to light olefin).
In one embodiment, described raw material comprises one or more thinner, typically is used to reduce material concentration, does not generally react with raw material or molecular sieve catalyst composition.The limiting examples of thinner comprise helium, argon, nitrogen, carbon monoxide, carbonic acid gas, water, basically nonreactive paraffins (especially paraffinic hydrocarbons such as methane, ethane and propane), basically nonreactive aromatic compound, and composition thereof.Most preferred thinner is water and nitrogen, particularly preferably is water.
The process that makes raw material especially comprise the feedstock conversion of one or more oxygenatedchemicals in the presence of molecular sieve catalyst composition of the present invention is carried out in reactor, described process is fixed bed process, fluidized bed process (comprising the turbulent bed method), preferred continuous fluidized bed method, most preferably continuous high speed fluidized bed process.
Described reaction process can various catalyticreactors if any be coupled at together tight bed or hybrid reactor, circulating fluid bed reactor and the riser reactor etc. of fixed bed reaction district and/or fast fluidized bed reaction zone in carry out.The popular response device type specification that is suitable for is at for example US4076 796, US6 287 522 (double lifting leg) and Fluidization Engineering, D.Kunii and O.Levenspiel, Robert E.Krieger Publishing Company, New York, New York, in 1977, all be incorporated herein for reference.
Preferred type of reactor is Riser Reactor, Fluidization andFluid-Particle Systems, p48-59, F.A.Zenz and D.F.Othmo, Reinhold Publishing Corp., riser reactor described in the USSN 09/,564 613 (multiple riser reactor) of NY 1960, US6 166 282 (fast fluidized bed reactor) and application on May 4th, 2000 all is incorporated herein for reference.
In the preferred embodiment, fluidized bed process or high-velocity fluidized bed method comprise reactor assembly, regeneration system rapidly and recovery system.
Described reactor assembly is preferably first reaction zone in one or more riser reactor and the fluidized bed reactor system of second reaction zone at least one separation vessel (preferably comprising one or more cyclonic separator).In one embodiment, described one or more riser reactor and separation vessel are included in the single reaction container.Fresh feed (preferably comprise one or more oxygenatedchemicals, one or more thinner is arranged alternatively) infeeds in one or more riser reactor, adds molecular sieve catalyst composition or its coking form in the described riser reactor.In one embodiment, described molecular sieve catalyst composition or its coking form and liquid or gas or its combination are contacted.Preferred described liquid is water or methyl alcohol, and described gas is rare gas element such as nitrogen.
Preferably in first reaction zone, make the raw material that enters reactor assembly partly or entirely change into gaseous effluent, enter separation vessel with pyrogenic molecular sieve catalyst composition.In the preferred embodiment, the cyclone design in the separation vessel becomes described molecular sieve catalyst composition, preferred pyrogenic molecular sieve catalyst composition are separated with the gaseous effluent that comprises one or more alkene.Cyclonic separator is preferred, but the gravitational effect in the separation vessel also will make catalyst composition separate with gaseous effluent.Isolating other method of catalyst composition and gaseous effluent is comprised utilize plate, lid and elbow etc.
In one of described separation system embodiment, described separation system comprises a separation vessel; Typically described separation vessel bottom is a stripping zone.In stripping zone, make pyrogenic molecular sieve catalyst composition contact the hydrocarbon that recovery is adsorbed from pyrogenic molecular sieve catalyst composition, introduce regeneration system rapidly then with gas, preferably water steam, methane, carbonic acid gas, carbon monoxide, hydrogen or one of rare gas element such as argon gas or combination (preferably water steam).In another embodiment, described stripping zone in the container that separates with described separation vessel, gas with based on gas volume than the volume 1 of coked molecular sieve catalyst composition to about 20000hr -1Gas hourly space velocity (GHSV) preferably under 250 to about 750 ℃, preferred about 350 to 650 ℃ high temperature by pyrogenic molecular sieve catalyst composition.
In the described conversion process, particularly in the described reactor assembly used invert point about 200 to about 1000 ℃, preferred about 250 to about 800 ℃, more preferably from about 250 to about 750 ℃, also more preferably from about 300 to about 650 ℃ in addition also more preferably from about 350 to about 600 ℃, most preferably from about 350 to about 550 ℃ scope.
In the described conversion process, used transfer pressure changes in comprising the wide region of autogenous pressure in the described reactor assembly particularly.Described transfer pressure is based on the dividing potential drop of raw material except that any thinner wherein.In the typically described process used transfer pressure about 0.1kPaa to about 5MPaa, preferably about 5kPaa extremely about 1MPaa, most preferably from about in 20 to about 500kPaa the scope.
Weight hourly space velocity (WHSV) particularly in reaction zone, in the presence of molecular sieve catalyst composition, make be defined as in the process of the feedstock conversion that comprises one or more oxygenatedchemicals enter reaction zone except that any thinner raw material gross weight/hour/reaction zone in the weight of molecular sieve in the molecular sieve catalyst composition.WHSV remains on is enough to make described catalyst composition to keep the level of fluidized state in reactor.
Typically, described WHSV about 1 to about 5000hr -1, preferred about 2 to about 3000hr -1, more preferably from about 5 to about 1500hr -1, most preferably from about 10 to about 1000hr -1Scope in.In one preferred embodiment, described WHSV is greater than 20hr -1The WHSV that is preferred for making the feedstock conversion that contains methyl alcohol and dme about 20 to about 300hr -1Scope in.
Raw material comprises that the empty tower gas velocity (SGV) of thinner and reaction product preferably is enough to make the molecular sieve catalyst composition fluidisation in the reaction zone in the reactor in the reactor assembly.In the described technology particularly in the reactor assembly, more especially the SGV in the riser reactor for 0.1m/s at least, be preferably greater than 0.5m/s, more preferably greater than 1m/s in addition more preferably greater than 2m/s in addition also more preferably greater than 3m/s, most preferably greater than 4m/s.Referring to for example USSN09/708 753 of application on November 8th, 2000, be incorporated herein for reference.
Make with the silicoaluminophosphamolecular molecular sieves catalyst composition in one of the method preferred embodiment of conversion of oxygenates to olefins, described process is at 20hr at least -1WHSV and less than 0.016, preferably be less than or equal to normalization method methane selectively (TCNMS) operation down of 0.01 temperature correction.Referring to for example US5 952 538, be incorporated herein for reference.
Pyrogenic molecular sieve catalyst composition takes out from separation vessel, preferably by one or more cyclonic separator, introduces regeneration system rapidly.Described regeneration system rapidly comprises revivifier, and pyrogenic catalyst composition is contacted under general regeneration temperature, pressure and residence time condition with regenerating medium (preferred oxygen-containing gas).
The limiting examples of described regenerating medium comprises oxygen, O 3, SO 3, N 2O, NO, NO 2, N 2O 5, air, with one or more of air, oxygen G﹠W (US6 245 703), carbon monoxide and/or the hydrogen of the dilution of nitrogen or carbonic acid gas.Regeneration condition is the coke incendiary condition that can make from the coking catalyst composition, preferably reaches based on the gross weight of the coked molecular sieve catalyst composition that the enters regeneration system rapidly level less than 0.5% (weight).The coked molecular sieve catalyst composition of taking out from revivifier constitutes regenerated molecular sieve catalyst composition.
Described regeneration temperature about 200 to about 1500 ℃, preferred about 300 to about 1000 ℃, more preferably from about 450 to about 750 ℃, most preferably from about in 550 to 700 ℃ the scope.Regeneration pressure at about 15psia (103kPaa) to about 500psia (3448kPaa), preferably about 20psia (138kPaa) is to about 250psia (1724kPaa), extremely about 150psia (1034kPaa), 30psia (207kPaa) extremely in the scope of about 60psia (414kPaa) most preferably from about of 25psia (172kPaa) more preferably from about.
The residence time of described molecular sieve catalyst composition in revivifier preferably about 1 minute to several hours, most preferably from about in 1 minute to 100 minutes the scope, the volume of oxygen is preferably in about scope of 0.01 to about 5mol%, based on the cumulative volume of gas in the described gas.
In one embodiment, regeneration accelerator (typically being metallic compound such as platinum and palladium etc.) for example adds in the revivifier with pyrogenic catalyst composition directly or indirectly.In another embodiment, fresh molecular sieve catalyst composition is added in the reactor of the regenerating medium that oxygen and water are housed, described in US6 245 703, be incorporated herein for reference.
In one embodiment, make a part of coked molecular sieve catalyst composition from revivifier (contact with raw material in advance or contact or contact) directly or indirectly and return one or more riser reactor with regenerated molecular sieve catalyst composition or refrigerative regenerated molecular sieve catalyst composition with the fresh molecular sieve catalyst composition.
Thereby from described conversion process, take out described molecular sieve catalyst composition in the described technological process and measure the coke content that its carbon content is measured molecular sieve catalyst composition.The coke content of the described molecular sieve catalyst composition in regeneration back is typically 0.01 to about 15% (weight), preferably about 0.1 to about 10% (weight), more preferably from about 0.2 to about 5% (weight), most preferably 0.3 to the scope of about 2% (weight), based on the gross weight of described molecular sieve but not the gross weight of described molecular sieve catalyst composition.
In one preferred embodiment, the mixture of fresh molecular sieve catalyst composition and regenerated molecular sieve catalyst composition and/or refrigerative regenerated molecular sieve catalyst composition is included in about 1 to 50% (weight), preferred about 2 to 30% (weights), more preferably from about 2 to about 20% (weight), most preferably from about 2 coke or carbonaceous sediments to about 10% scope, based on the gross weight of the mixture of molecular sieve catalyst composition.Referring to for example US6 023 005, be incorporated herein for reference.
Described gaseous effluent is discharged from separation system and is passed through recovery system.There are many known recovery systems, technology and sequence to be applicable to and from described gaseous effluent, separate alkene and make the alkene purifying.Recovery system generally comprises various separation, fractionation and/or distillation tower, post, equipment or unit, one or more of the production (US5 675 041) of the processing of reactive system such as ethylbenzene production (US5 476 978) and other derivative such as aldehyde, ketone and ester and for example various condensers of other equipment that accompanies, interchanger, refrigerating system or cooling unit, compressor, knockout drum or jar and pump etc. or combination.
Molecular screen material of the present invention and catalyst composition can be used for producing alkylamine, utilize ammonia.The example of appropriate methodology is described among EP 0 993 867 A1 and the US6 153 798 (Hidaka etc.), is incorporated herein for reference.
The present invention includes its typical advantages for understanding better, following examples are provided.
Embodiment
XRD
Record X-ray powder diffraction pattern on the Siemens D500 of 40kV voltage and 30mA electric current diffractometer, and use Cu target and Ni-strainer (λ=0.154nm).Carry out the ultimate analysis of Al, Si and P with inductively coupled plasma (ICP) Spectrum Method.
Embodiment 1
Prepare by the following method and characterize eight samples.
Following composition is mixed successively and (Tissue Tearor Model98730, available from Biospec Products, Inc. USA) is mixed into even gel: 85wt%H with miniature homogenizer 3PO 4(from Aldrich Chemical Company), H 2O, Cabosil TM(from CabotCorporation Illinois, USA), Catapal TMA (74wt%Al 2O 3, from CONDEAVista Company, Texas, USA) and N, N-dimethylcyclohexylamine (DMCHA; (CH 3) 2NC 6H 11From Aldrich Chemical Company, USA).The mol ratio of these compositions is as follows:
2.0?DMCHA∶1.0?Al 2O 3∶x?SiO 2∶1.0?P 2O 5∶40?H 2O
X=0,0.1,0.2 and 0.3
Under the situation of x=0.1, earlier to 5.65g H 3PO 4The middle 14.58g deionized water that adds.Under agitation add 3.38g Catapal then in succession lentamente TMA, 0.16g Cabosil TMWith 6.23g N, the N-dimethylcyclohexylamine forms gel.Handle the even gel of described gel formation with miniature homogenizer.The pH that measures described gel with pH paper is 5.This gel is divided into two five equilibriums, all is sealed in the autoclave of teflon lining.Described autoclave is placed in the baking oven, and temperature is set in 180 ℃.Described autoclave took out from baking oven after 3 days and 7 days respectively.After the cooling, the pH that measures supernatant liquor is 9.
With the solid phase prod centrifugation in the autoclave, wash several times with deionized water, be lower than 50S/cm until the specific conductivity of washing lotion, then dried overnight in 60 ℃ of vacuum drying ovens.Consumption by changing the silicon source prepares mixture to the molecular sieve of x=0, x=0.2 and x=0.3 and repeats this step.What crystallization obtained after 3 days is shown among Fig. 1 by the X-ray powder diffraction pattern of x=0,0.1,0.2 and 0.3 molecular sieve synthetic mixture products obtained therefrom respectively.Table I b lists the XRD peak of molecular sieve synthetic mixture crystallization products obtained therefrom after 3 days of x=0.1.
Table I b
??2θ ??d(A) ????I％
??9.46 ??9.34 ????63
??12.86 ??6.88 ????12
??13.98 ??6.33 ????16
??16.02 ??5.53 ????51
??17.80 ??4.98 ????24
??19.06 ??4.65 ????2
??20.62 ??4.30 ????100
??22.06 ??4.03 ????8
??22.42 ??3.96 ????11
??23.10 ??3.85 ????7
??25.02 ??3.56 ????36
??25.96 ??3.43 ????16
??27.72 ??3.22 ????4
??28.26 ??3.16 ????4
??29.62 ??3.01 ????4
??30.68 ??2.91 ????37
??31.18 ??2.87 ????18
??31.68 ??2.82 ????2
??32.44 ??2.76 ????2
??33.62 ??2.66 ????3
??34.60 ??2.59 ????8
??35.02 ??2.56 ????1
??36.18 ??2.48 ????5
??38.76 ??2.32 ????1
??39.84 ??2.26 ????3
??42.98 ??2.10 ????3
??43.58 ??2.08 ????3
??45.28 ??2.00 ????1
??46.92 ??1.93 ????1
??47.84 ??1.90 ????4
??49.02 ??1.86 ????4
??49.52 ??1.84 ????1
The XRD figure of Fig. 1 show x=0.1,0.2 or 0.3 crystalline mixture after 3 days products obtained therefrom be the silicon aluminium phosphate of pure CHA framework types.The crystalline mixture of x=0.0 after 3 days products obtained therefrom appear as the mixture of the aluminum phosphate of ALPO-5 and CHA framework types.
The X-ray powder diffraction pattern of crystallization gained x=0,0.1,0.2 and 0.3 product after 7 days is shown among Fig. 2.The XRD figure of Fig. 2 showed crystallization after 7 days, and the molecular sieve of x=0.1 prepares the crystalline impurities that mixture forms the AFI framework types on a small quantity.X=0.2 or 0.3 molecular sieve prepare the pure phosphoric acid Si-Al molecular sieve that mixture produces the CHA framework types.The product yield (being expressed as the weight percent of the finished product with respect to initial gel weight) and the chemical constitution of product by determination of elemental analysis are shown in the Table II.
Result shown in Fig. 1, Fig. 2, Table I b and the Table II shows can be by comprising N, and the N-dimethylcyclohexylamine prepares the pure phosphoric acid sial of mixture with the good low Si content of yield preparation as the molecular sieve of organic formwork agent.These results also show with this template also can prepare ALPOs, although some is impure.
Table II
Crystallization time (my god) Molecular sieve prepares the composition of mixture
??x＝0 ??x＝0.1 ??X＝0.2 ??X＝0.3
????3 Yield ??13.2 * ??14.1 ??17.0 ??18.6
????3 Product is formed ??- ??AlSi 0.07P 0.943 ??AlSi 0.119P 0.881 ??AlSi 0.154P 0.866
????3 The Si/CHA cage ??- ??0.42 ??0.714 ??0.924
????7 Yield ??15.0 * ??16.1 * ??17.1 ??19.3
*Impure
Embodiment 2
Prepare by the following method and characterize four samples.
Following composition is mixed successively and (Tissue Tearor Model98730, from Biospec Products, Inc. USA) is mixed into even gel: 85wt%H with miniature homogenizer 3PO 4(from Aldrich Chemical Company), H 2O, Cabosil TM(from CabotCorporation Illinois, USA), Catapal TMA (74wt%Al 2O 3, from CONDEAVista Company, Texas, USA) and N, N-dimethylcyclohexylamine (DMCHA) is (from Aldrich Chemical Company, USA).At last, (50% aqueous solution is from Aldrich Chemical Company, USA) as last composition to add HF in synthesized gel rubber.The mol ratio of these compositions is as follows:
0.5?HF∶2.0?DMCHA∶1.0?Al 2O 3∶x?SiO 2∶1.0?P 2O 5∶40?H 2O
X=0,0.1,0.2 and 0.3
Press the method for embodiment 1, Tc is 180 ℃, and crystallization time is 3 days.What crystallization obtained after 3 days is shown among Fig. 3 by the X-ray powder diffraction pattern of x=0,0.1,0.2 and 0.3 molecular sieve synthetic mixture products obtained therefrom respectively.Table III b lists the XRD peak of molecular sieve synthetic mixture crystallization products obtained therefrom after 3 days of x=0.1.
Table III b
??2θ ??d(A) ????I％
??9.54 ??9.26 ????100
??12.92 ??6.85 ????9
??13.36 ??6.62 ????4
??14.04 ??6.30 ????20
??14.56 ??6.08 ????3
??15.68 ??5.65 ????15
??16.08 ??5.51 ????57
??16.80 ??5.27 ????8
??17.88 ??4.96 ????25
??18.00 ??4.92 ????27
??20.68 ??4.29 ????76
??21.22 ??4.18 ????21
??22.12 ??4.02 ????7
??22.60 ??3.93 ????8
??23.18 ??3.83 ????4
??25.04 ??3.55 ????32
??25.44 ??3.50 ????20
??26.00 ??3.42 ????10
??26.26 ??3.39 ????3
??27.00 ??3.30 ????3
??28.28 ??3.15 ????4
??30.36 ??2.94 ????9
??30.74 ??2.91 ????22
??31.04 ??2.88 ????26
??31.18 ??2.87 ????19
??31.60 ??2.83 ????9
??33.64 ??2.66 ????3
??34.60 ??2.59 ????5
??36.24 ??2.48 ????5
??43.02 ??2.10 ????4
The XRD figure of Fig. 3 show x=0.1,0.2 or 0.3 crystalline mixture after 3 days products obtained therefrom be the silicon aluminium phosphate of pure CHA framework types.The crystalline mixture of x=0.0 after 3 days products obtained therefrom appear as the mixture of the aluminum phosphate of ALPO4-5 and CHA framework types.Obviously exist fluorochemical to make crystalline structure that some small distortion take place, cause diffraction peak more and wideer.SiO 2Measure highly more, be out of shape more little.
The product yield (being expressed as the weight percent of the finished product with respect to initial gel weight) and the chemical constitution of product by determination of elemental analysis are shown in the Table IV.
Table IV
The yield product is formed Molecular sieve prepares the composition of mixture
????x＝0 ????X＝0.1 ????X＝0.2 ????X＝0.3
Yield ????15.7 * ????15.7 ????18.9 ????17.9
Product F/Al ????0.1136 ????0.0872 ????0.0805 ????0.0500
Si/Al in the product ????0 ????0.059 ????0.077 ????0.132
The Si/CHA cage ????0 ????0.354 ????0.462 ????0.792
One of skill in the art will recognize that and under the situation that does not deviate from spirit and scope of the invention, to carry out many modifications.Specific embodiments described herein only is will illustrate and should not be construed as restriction the present invention

Claims (26)

1. the preparation method of the crystalline molecular sieve of a CHA framework types, described method comprises:
A) provide the synthetic mixture of the organic formwork agent that comprises aluminium source, phosphorus source, silicon source and at least a formula (I)
R 1R 2N-R 3???????????(I)
Wherein
-R 1And R 2Be independently selected from the alkyl and the hydroxyalkyl that 1 to 3 carbon atom is arranged of 1 to 3 carbon atom;
-R 3Be selected from alternatively 4-to the 8-unit cycloalkyl that replaced by 1 to 3 alkyl that 1 to 3 carbon atom arranged, 1 to 3 heteroatomic 4-to 8-unit heterocyclic radical is arranged, described heterocyclic radical is had the alkyl of 1 to 3 carbon atom to replace by 1 to 3 alternatively, and the heteroatoms in the described heterocyclic radical is selected from O, N and S; With
B) make crystalline molecular sieve crystallization from described reaction mixture of CHA framework types.
2. the process of claim 1 wherein that the organic formwork agent of formula (I) is the template of formula (II)
(CH 3) 2N-R 3????????????????(II)
R wherein 3For alternatively by 1 to 3 methyl substituted 4-to 8-unit cycloalkyl.
3. arbitrary method of aforementioned claim, wherein R 3For alternatively by 1 to 3 methyl substituted cyclohexyl.
4. arbitrary method of aforementioned claim, wherein said organic formwork agent is selected from N, N-dimethyl-hexahydroaniline, N, N-dimethyl-cyclopentamine, N, N-dimethyl-methyl cyclohexylamine and N, N-dimethyl-methyl cyclopentamine.
5. arbitrary method of aforementioned claim, wherein said organic formwork agent are N, N-dimethyl-hexahydroaniline.
6. arbitrary method of aforementioned claim, wherein said synthetic mixture also comprises at least a fluoride sources.
7. the method for claim 6, wherein said fluoride sources is a hydrogen fluoride.
8. arbitrary method of aforementioned claim, the organic formwork agent that wherein comprises cationic organic formwork agent of Tetrylammonium and formula (I) is used in combination.
9. the method for claim 8, the wherein said cationic organic formwork agent of Tetrylammonium that comprises is selected from tetraethylammonium chloride, tetraethyl-ammonium bromide, fluoridizes Tetrylammonium and composition thereof.
10. arbitrary method of aforementioned claim, the mol ratio of template and aluminium template and aluminum oxide (Al in the wherein said synthetic mixture 2O 3) mol ratio when representing in 1.0: 1.0 to 3.0: 1.0 scope.
11. arbitrary method of aforementioned claim, the mol ratio of template and aluminium template and aluminum oxide (Al in the wherein said synthetic mixture 2O 3) mol ratio when representing in 1.5: 1.0 to 3.0: 1.0 scope.
12. arbitrary method of aforementioned claim also comprises and reclaiming and the crystalline molecular sieve of the described CHA framework types of roasting provides the step of the silicon aluminium phosphate of activatory CHA framework types.
13. a silicoaluminophosphamolecular molecular sieves is the CHA framework types basically, comprises the template of at least a formula (I) in its intracrystalline structure
R 1R 2N-R 3??????????(I)
Wherein
-R 1And R 2Be independently selected from the alkyl and the hydroxyalkyl that 1 to 3 carbon atom is arranged of 1 to 3 carbon atom;
-R 3Be selected from alternatively 4-to the 8-unit cycloalkyl that replaced by 1 to 3 alkyl that 1 to 3 carbon atom arranged, 1 to 3 heteroatomic 4-to 8-unit heterocyclic radical is arranged, described heterocyclic radical is had the alkyl of 1 to 3 carbon atom to replace by 1 to 3 alternatively, and the heteroatoms in the described heterocyclic radical is selected from O, N and S.
14. a silicoaluminophosphamolecular molecular sieves is the CHA framework types basically, comprises the template of at least a formula (II) in its intracrystalline structure
(CH 3) 2N-R 3?????????(II)
Wherein
-R 3For alternatively by 1 to 3 methyl substituted 4-to 8-unit cycloalkyl.
15. a silicoaluminophosphamolecular molecular sieves is the CHA framework types basically, comprises N in its intracrystalline structure, N-dimethyl-hexahydroaniline.
16. the silicoaluminophosphamolecular molecular sieves of claim 15 also comprises fluorochemical.
17. a crystallization silicoaluminophosphamolecular molecular sieves, its characteristic X-ray powder diagram comprises d-spacing shown in the Table I a at least.
18. a crystallization silicoaluminophosphamolecular molecular sieves, its characteristic X-ray powder diagram comprises d-spacing shown in the Table I b at least.
19. arbitrary molecular sieve of claim 17 or 18 comprises N in its intracrystalline structure, N-dimethyl-hexahydroaniline.
20. a crystallization silicoaluminophosphamolecular molecular sieves, its characteristic X-ray powder diagram comprises d-spacing shown in the Table III a at least.
21. a crystallization silicoaluminophosphamolecular molecular sieves, its characteristic X-ray powder diagram comprises d-spacing shown in the Table III b at least.
22. arbitrary molecular sieve of claim 20 or 21, it comprises N in the intracrystalline structure, N-dimethyl-hexahydroaniline and fluorochemical.
23. the preparation method of a molecular sieve catalyst composition comprises making the arbitrary described of at least a claim 13 to 22 or making up with at least a preparaton by the molecular sieve of either party's method of claim 1 to 12 preparation.
24. the molecular sieve catalyst composition of a preparation comprises with the arbitrary described of at least a claim 13 to 22 of at least a preparaton blended or by the molecular sieve of either party's method of claim 1 to 12 preparation.
25. the arbitrary described molecular sieve of claim 13 to 22 or be used to make as catalyzer by the molecular sieve catalyst composition of the molecular sieve of either party's method of claim 1 to 12 preparation or the described preparation of claim 24 and contain the purposes that the oxygen feedstock conversion becomes one or more alkene.
26. one kind makes and contains the method that the oxygen feedstock conversion becomes one or more alkene, comprises the step that makes the described arbitrary described molecular sieve that contains oxygen raw material and claim 13 to 22 or contact by the molecular sieve catalyst composition of the molecular sieve of either party's method preparation of claim 1 to 12 or the described preparation of claim 24.
CNB038134950A 2002-06-12 2003-06-11 Synthesis of aluminophosphates and silicoaluminophosphates Expired - Fee Related CN1302989C (en)

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US10/170,293 US6680278B2 (en) 2002-06-12 2002-06-12 Synthesis of silicoaluminophosphates
US10/171,186 US6620983B1 (en) 2002-06-12 2002-06-12 Synthesis of aluminophosphates and silicoaluminophosphates
US10/170,293 2002-06-12
US10/171,257 2002-06-12
US10/171,257 US6793901B2 (en) 2002-06-12 2002-06-12 Synthesis of molecular sieves having the CHA framework type
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US10/422,923 US6914030B2 (en) 2002-06-12 2003-04-24 Synthesis of silicoaluminophosphates

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CN100372760C (en) * 2005-09-14 2008-03-05 南开大学 12-ring large micropore aluminum phosphite molecular sieve and preparation method
CN100395184C (en) * 2006-03-23 2008-06-18 南开大学 Synthesis method of silicon aluminium phosphate molecular sieve
CN103663484A (en) * 2012-09-26 2014-03-26 中国科学院大连化学物理研究所 Method for quickly synthesizing SAPO(silicoaluminophosphate)-34 molecular sieve and catalyst prepared from molecular sieve

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US10118166B2 (en) * 2014-06-06 2018-11-06 Uop Llc Zeolitic materials with modified surface composition, crystal structure, crystal size, and/or porosity, methods for making the same, and methods for converting oxygenates to olefins via reactions catalyzed by the same
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CN100395184C (en) * 2006-03-23 2008-06-18 南开大学 Synthesis method of silicon aluminium phosphate molecular sieve
WO2008019583A1 (en) * 2006-08-08 2008-02-21 Dalian Institute Of Chemical Physics Chinese Academy Of Sciences A PROCESS FOR SYNTHESIZING SAPO-34 MOLECULAR SIEVE ENRICHED WITH A Si(4Al) STRUCTURE IN THE SKELETON
CN103663484A (en) * 2012-09-26 2014-03-26 中国科学院大连化学物理研究所 Method for quickly synthesizing SAPO(silicoaluminophosphate)-34 molecular sieve and catalyst prepared from molecular sieve
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