US20100196262A1 - Sapo-34 molecular sieve having both micropores and mesopores and synthesis methods thereof - Google Patents

Sapo-34 molecular sieve having both micropores and mesopores and synthesis methods thereof Download PDF

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US20100196262A1
US20100196262A1 US12/302,728 US30272807A US2010196262A1 US 20100196262 A1 US20100196262 A1 US 20100196262A1 US 30272807 A US30272807 A US 30272807A US 2010196262 A1 US2010196262 A1 US 2010196262A1
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molecular sieve
sapo
synthesis method
micropores
mesopores
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Lei Xu
Peng Tian
Zhongmin Liu
Lixin Yang
Shuanghe Meng
Changqing He
Cuiyu Yuan
Yue Qi
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • 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
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/10—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least phosphorus atoms
    • 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
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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

  • the present invention relates to a SAPO-34 molecular sieve having both micropores and mesopores, and the mesopore diameter of the molecular sieve is in a range of 2-10 nm and the pore volume thereof is 0.03-0.3 cm 3 /g, as well as the synthesis method of the molecular sieve.
  • the molecular sieve prepared by this method is used for the catalysis of the conversion reaction of oxygen-containing compounds to lower olefins.
  • micropore-mesopore composite molecular sieves having double grade pores of micropores and mesopores have incorporated the pore advantage of mesopore materials with the strong acidic property and the high hydrothermal stability of micropore molecular sieves and made both of the materials complementary and cooperative. Furthermore, the pore diameter and acidic property are both adjustable, that is, a composite material with different pore allocations and acidic property distributions can be prepared by performing an optimized combination of two selected materials with different pore structures and acidic properties.
  • the successful preparation and versatile modes of the molecular sieves with multi-grade pores characterized in assembly will have a wide application perspective in more fields (Nature, 417 (2002) 813).
  • micropore-mesopore composite molecular sieves have two types of composite modes: (1) a composite of two materials of micropore molecular sieve and mesopore molecular sieve.
  • the two materials of micropore molecular sieve and mesopore molecular sieve often show a coating structure, an embedding structure, or a complex combination of both of the structures.
  • an obvious connected interface is present between the two materials and the results characterized by X-ray diffraction (XRD) will show the diffraction peaks corresponding to the two materials, respectively;
  • XRD X-ray diffraction
  • this type of composite mode includes two manners: a micropore molecular sieve with mesopores, that is, a micropore molecular sieve introduced with mesopores, contributes to the diffusion of molecules while maintaining the strong acidic property and stability of the micropore molecular sieve; a mesopore molecular sieve with parts of the properties of micropore molecular sieve, that is, a mesopore material whose amorphous pore walls have been introduced with a primary or secondary
  • SAPO-34 molecular sieve was disclosed in U.S. Pat. No. 4,440,871 in 1984. According to the definition of IUPAC on pore diameter size, SAPO-34 belongs to the small pore molecular sieves ( ⁇ 2 nm). SAPO-34 molecular sieve has attracted attention because it has shown superior catalysis performance in the conversion reaction of methanol to olefins (MTO).
  • MTO methanol to olefins
  • An object of the present invention is to provide a SAPO-34 molecular sieve having both micropores and mesopores and the synthesis method thereof.
  • the technical solution of the present invention is to provide a SAPO-34 molecular sieve having both micropores and mesopores, and the mesopore diameter of the molecular sieve is 2-10 nm and the mesopore volume thereof is 0.03-0.3 cm 3 /g.
  • the surface of the cubic crystal type molecular sieve thereof is rough or broken.
  • Said synthesis method includes the following steps:
  • step b) A pore size modifier is added into the initial gel mixture obtained in step a) and stirred sufficiently;
  • step c) The gel mixture obtained in step b) is sealed and heated to crystallization temperature, and a thermostatic crystallization is performed under autogenous pressure; after the crystallization is completed, a solid product is separated, washed to be neutral and dried, and thus as-synthesized SAPO-34 molecular sieve is obtained.
  • step c) The as-synthesized SAPO-34 molecular sieve obtained in step c) is calcined in air to remove the organics contained in the material, and a SAPO-34 molecular sieve having both micropores and mesopores is obtained.
  • the oxide molar proportions of all components in said initial synthesis gel mixture are:
  • said pore size modifier is one or more selected from the group consisted of aqueous ammonia, tetramethylammonium hydroxide, diethylamine, tripropylamine, di-n-propylamine, n-propylamine, n-butylamine, cyclohexylamine and a mixture thereof.
  • the crystallization temperature in step c) is 100-250° C.
  • the preferable crystallization temperature is 160-230° C.
  • the crystallization time in step c) is 0.5 ⁇ 100 h, and the preferable crystallization time is 2-48 h.
  • SAPO-34 molecular sieve it is used as a catalyst for the conversion of oxygen-containing compounds to lower olefins.
  • the SAPO-34 molecular sieve having both micropores and mesopores synthesized in the present invention as the catalyst for MTO reaction, due to the presence of a hierachical structure, the influence on diffusion mass transfer can be reduced or eliminated, the occurrence of secondary reaction can be decreased, and therefore the catalyst life can be prolonged, as well as the selectivity for ethylene and propylene can be increased, greatly.
  • FIG. 1 The XRD spectra of the SAPO-34 synthesized in example 1, 3, 4, 5 added with a pore size modifier and in comparative example 1 without the addition of a pore size modifier.
  • FIG. 2 In this figure, FIG. 2 a , FIG. 2 b , FIG. 2 c , FIG. 2 d and FIG. 2 e are the SEM photos of the samples in example 1, 3, 4, 5 and comparative example 1 of the present invention.
  • FIG. 3 In this figure, FIG. 3 a and FIG. 3 b are the schematic diagrams of nitrogen adsorption isotherms and mesopore distributions of the samples with the numbers of MSP34-1 and SP34 in example 2 of the present invention (adsorption line branch, BJH method).
  • FIG. 4 In this figure, FIG. 4 a and FIG. 4 b are the schematic diagrams of nitrogen adsorption isotherms and mesopore distributions of the samples with the numbers of MSP34-2, -3 and -4 in example 6 of the present invention (adsorption line branch, BJH method).
  • the present invention is characterized in that the synthesized SAPO-34 molecular sieve has a mesopore pore diameter of 2-10 nm and a mesopore volume of 0.03-0.3 cm 3 /g.
  • the present invention is characterized in that the surface of cubic crystals of the synthesized SAPO-34 molecular sieve can be rough or broken.
  • the present invention is characterized in that triethylamine is used as a template agent and a pore size modifier is added into a synthesis gel.
  • the present invention provides a synthesis method of a SAPO-34 molecular sieve having both micropores and mesopores, and the preparation process is as follows:
  • the pore size modifier is one or more selected from the group consisted of aqueous ammonia, tetramethylammonium hydroxide, diethylamine, tripropylamine, di-n-propylamine, n-propylamine, n-butylamine, cyclohexylamine and a mixture thereof.
  • step b) The gel mixture obtained in step b) is loaded into a stainless steel autoclave lined with polytetrafluoroethylene inside, sealed and then heated to crystallization temperature, and a thermostatic crystallization is performed under autogenous pressure with a crystallization temperature of 100-250° C. and a crystallization time of 5-100 h. After the crystallization is completed, a solid product is separated by centrifugation, washed to be neutral with deionized water and dried in air at 120° C., and thus as-synthesized SAPO-34 molecular sieve is obtained.
  • step b) The as-synthesized SAPO-34 molecular sieve obtained in step b) is calcined in air to remove the organics and a SAPO-34 molecular sieve with a distribution of micropores and mesopores is obtained.
  • a gel was formed by sufficient stirring, loaded into a stainless steel autoclave lined with polytetrafluoroethylene inside, sealed and heated to 200° C., and under autogenous pressure, a thermostatic crystallization was performed for 12 h. Then a solid product was separated by centrifugation, washed to be neutral with deionized water and dried in air at 120° C., and thus a SAPO-34 molecular sieve was obtained. After calcined the as-synthesized sample at 600° C. for 4 h to remove the template agent, a SAPO-34 molecular sieve having micropores and mesopores was obtained (the number was MSP34-1). The XRD pattern of the as-synthesized sample was shown in FIG. 1 and the SEM photo thereof was shown in FIG. 2 . It can be seen that the surface of cubic crystals of MSP34-1 sample was rough or broken.
  • Gauged raw materials were mixed in a certain sequence in an initial gel molar proportion of 3.0 TEA:0.4 SiO 2 :P 2 O 5 :Al 2 O 3 :50 H 2 O, and all the raw materials used were TEA (analytical pure), silica sol (SiO 2 content is 30 wt %), pseudobochmite (Al 2 O 3 content is 70 wt %) and phosphoric acid (H 3 PO 4 content is 85 wt %).
  • a gel was formed by sufficient stirring, loaded into a stainless steel synthetic kettle lined with polytetrafluoroethylene inside, sealed and heated to 200° C., and under autogenous pressure, a thermostatic crystallization was performed for 12 h.
  • the sample with a number of MSP34-1 obtained in example 1 and the sample with a number of SP34 obtained in comparative example 1 were subjected to a nitrogen physical adsorption characterization to measure the specific surface areas and the pore structures of the molecular sieves.
  • the nitrogen adsorption isotherms and the mesopore distributions were shown in FIG. 3 and the specific surface areas and the pore volumes were shown in Table 1.
  • MSP34-1 sample had a mesopore distribution with a mesopore pore diameter of 2.3 nm and a mesopore volume of 0.07 cm 3 /g.
  • a gel was formed by sufficient stirring, loaded into a stainless steel autoclave lined with polytetrafluoroethylene inside, sealed and heated to 200° C., and under autogenous pressure, a thermostatic crystallization was performed for 12 h. Then a solid product was separated by centrifugation, washed to be neutral with deionized water and dried in air at 120° C., and thus a SAPO-34 molecular sieve was obtained. After calcined the sample at 600° C. for 4 h to remove the template agent, a SAPO-34 molecular sieve having micropores and mesopores was obtained (the number was MSP34-2). The XRD pattern of the as-synthesized sample was shown in FIG. 1 and the SEM photo thereof was shown in FIG. 2 . It can be seen that the surface of cubic crystals of MSP34-2 sample was rough or broken.
  • a gel was formed by sufficient stirring, loaded into a stainless steel autoclave lined with polytetrafluoroethylene inside, sealed and heated to 200° C., and under autogenous pressure, a thermostatic crystallization was performed for 12 h. Then a solid product was separated by centrifugation, washed to be neutral with deionized water and dried in air at 120° C., and therefore a SAPO-34 molecular sieve was obtained. After calcined the raw power at 600° C. for 4 h to remove the template agent, a SAPO-34 molecular sieve having micropores and mesopores was obtained (the number was MSP34-3). The XRD pattern was shown in FIG. 1 and the SEM photo was shown in FIG. 2 . It can be seen that the surface of cubic crystals of MSP34-3 sample was rough.
  • a gel was formed by sufficient stirring, loaded into a stainless steel synthetic kettle lined with polytetrafluoroethylene inside, sealed and heated to 200° C., and under autogenous pressure, a thermostatic crystallization was performed for 12 h. Then a solid product was separated by centrifugation, washed to be neutral with deionized water and dried in air at 120° C., and thus a SAPO-34 molecular sieve was obtained. After calcined the raw power at 600° C. for 4 h to remove the template agent, a SAPO-34 molecular sieve having micropores and mesopores was obtained (the number was MSP34-4). The XRD pattern of the as-synthesized sample was shown in FIG. 1 and the SEM photo thereof was shown in FIG. 2 . It can be seen that the surface of cubic crystals of MSP34-4 sample was rough or broken.
  • the samples with numbers of MSP34-2, -3 and -4 obtained in example 3, 4 and 5 were subjected to a nitrogen physical adsorption characterization to measure the specific surface areas and the pore structures of the molecular sieves.
  • the nitrogen adsorption isotherms and the mesopore distributions were shown in FIG. 4 and the specific surface areas and the pore volumes were shown in Table 1.
  • the mesopore volumes of the three samples were 0.09, 0.06 and 0.14 cm 3 /g, respectively.
  • the sample with a number of MSP34-1 obtained in example 1 and the sample with a number of SP34 obtained in comparative example 1 were calcined at 600° C. for 4 h under air, then pressed and sieved to a mesh of 20 ⁇ 40.
  • 1.0 g of a sample was weighed and loaded into a fixed bed reactor to carry out a MTO reaction evaluation.
  • the sample was activated at 550° C. for 1 h under nitrogen gas and then reduced to 450° C. to perform a reaction.
  • Methanol was carried by nitrogen gas with a flow rate of 40 ml/min and the weight space rate of methanol was 4.0 h ⁇ 1 .
  • the reaction products were analyzed by an on-line gas chromatograph and the results were shown in Table 2.

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Cited By (7)

* Cited by examiner, † Cited by third party
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CN102614910A (zh) * 2012-03-16 2012-08-01 北京工业大学 用于氨选择性催化消除NOx的SAPO-34负载Cu-Fe催化剂的制备方法
CN102992349A (zh) * 2012-12-11 2013-03-27 陕西煤化工技术工程中心有限公司 一种sapo-34分子筛合成母液的循环利用方法
CN106276945A (zh) * 2015-06-10 2017-01-04 中国科学院大连化学物理研究所 一种具有中、微孔复合孔道结构的rho-sapo分子筛
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CN117699814A (zh) * 2022-09-02 2024-03-15 国家能源投资集团有限责任公司 一种多孔、低硅sapo-34分子筛的制备方法及用途
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