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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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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  • 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
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  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
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  • 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)
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  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—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
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  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/06—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
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  • 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

• SAPO-34 molecular sieve with microporous and mesoporous structure and synthesis method
• the invention relates to a SAPO-34 molecular sieve having a microporous and mesoporous structure, wherein the pore diameter ranges from 2 to 10 nm, the mesopore volume is from 0.03 to 0.3 cm 3 /g, and the molecular sieve is synthesized, and the molecular sieve prepared by the method Catalyst for the conversion of oxygenates to light olefins. Background technique
• the microporous-mesoporous composite molecular sieve has microporous and mesoporous two-stage pores, which combines the pore advantage of the mesoporous material with the strong acidity and high hydrothermal stability of the microporous molecular sieve, so that the two materials have complementary advantages and synergistic effects. Moreover, both the pore size and the acidity can be adjusted, that is, by selecting two materials of different pore structure and acid properties for optimal compounding, composite materials with different pore configurations and acid distributions can be prepared. The successful preparation and diversification of multi-stage molecular sieve materials characterized by assembly will have broad application prospects in more fields (Nature, 417 (2002) 813).
• microporous-mesoporous composite molecular sieves have two major types of composite modes: (1) the combination of microporous molecular sieves and mesoporous molecular sieves.
• the microporous molecular sieve and the mesoporous molecular sieve are often in a cladding structure, a mosaic structure, or a complex combination of the two structures. At this time, there is a clear connection interface (transition layer) between the two materials.
• X-ray diffraction (XRD) characterization results will show the corresponding diffraction peaks of the two materials at the same time;
• the mesopores and micropores are in a kind Composite in molecular sieve materials, such composite mode contains two forms: microporous molecular sieves with mesopores, ie, mesopores introduced into microporous molecular sieves, which are beneficial to molecules while retaining the strong acidity and stability of microporous molecular sieves.
• a mesoporous molecular sieve having the properties of a microporous zeolite molecular sieve that is, introducing a primary or secondary structural unit of the zeolite into the amorphous pore wall of the mesoporous material to achieve a pore wall in the nanometer range.
• Detailed research progress in this area is described in Petrochemicals (02 (2005) 188). So far, all reported mesoporous microporous composite molecular sieves are molecular sieve systems composed of silicon-aluminum, and for molecular sieve systems composed of silicon-phosphorus-aluminum, due to the complexity of the synthetic system, no publicly available literature has been reported.
• SAPO-34 molecular sieves were published in 1984 by USP 4,440,871. According to IUPAC's definition of pore size, SAPO-34 is a small pore molecular sieve ( ⁇ 2nm). SAPO-34 molecular sieves have attracted attention due to their excellent catalytic performance in methanol conversion to alkylene reaction (MTO). Summary of the invention
• the object of the present invention is to provide a SAPO-34 molecular sieve having a microporous mesoporous structure and a synthesis method thereof.
• the molecular sieve is used as a catalyst for the MTO reaction, which can reduce or eliminate the limitation of diffusion mass transfer and reduce the occurrence of secondary reactions. Thereby prolonging the catalyst life and increasing the selectivity of ethylene propylene.
• the technical solution of the present invention is to provide a SAPO-34 molecular sieve having a microporous and mesoporous structure, the molecular sieve having a mesopores of 2 to 10 nm and a mesopore volume of 0.03 to 0.3 cm 3 /g.
• the SAPO-34 molecular sieve has a cubic molecular sieve grain surface which is rough or damaged.
• a method of synthesizing the SAPO-34 molecular sieve using triethylamine as a templating agent while adding a channel modifier to the synthetic gel is described.
• the synthesis method includes the following steps:
• step b) adding a channel regulator to the initial gel mixture obtained in step a) and stirring well; c) sealing the gel mixture obtained in step b), then heating to the crystallization temperature, and thermostating under autogenous pressure Crystallization; after the crystallization is completed, the solid product is separated, washed to neutral, and dried to obtain a raw powder of SAPO-34 molecular sieve:
• step c) The raw material of SAPO-34 molecular sieve obtained in step c) is calcined in air to remove the organic matter contained in the original powder to obtain SAPO-34 molecular sieve having both microporous and mesopores.
• the molar ratio of each component oxide in the initial synthetic gel mixture is:
• TEA/ A1 2 0 3 1 to 5 (TEA is triethylamine).
• the channel regulator is one or more of ammonia water, tetramethylammonium hydroxide, diethylamine, tripropylamine, di-n-propylamine, n-propylamine, n-butylamine or cyclohexylamine. mixture.
• the crystallization temperature in the step c) is 100-250 ° C, and the preferred crystallization temperature is 160-230 ° C.
• the crystallization time in the step c) is 0.5 to 100 hours, and the preferred crystallization time is 2 to 48 hours.
• the SAPO-34 molecular sieve is used as a catalyst for the conversion of oxygenates to light olefins.
• the SAPO-34 molecular sieve having the microporous mesoporous structure synthesized by the invention is used as a catalyst for the MTO reaction, and the influence of the diffusion mass transfer is greatly reduced or eliminated due to the existence of the two-stage pore structure, thereby reducing the occurrence of the secondary reaction and thereby prolonging the catalyst. Life expectancy and increase the selectivity of ethylene propylene.
• Figure 2 wherein Figures 2a, 2b, 2c, 2d, and 2e are SEM photographs of samples in Examples 1, 3, 4, 5 and Comparative Example 1 of the present invention
• Fig. 3 Fig. 3a and Fig. 3b are schematic diagrams showing the distribution of nitrogen adsorption isotherms and mesopores of samples No. MSP34-1 and SP34 in Example 2 of the present invention (adsorption line branching, BJH method).
• Fig. 4 wherein Fig. 4a and Fig. 4b are schematic diagrams showing the nitrogen adsorption isotherms and mesopores of the samples numbered MSP34-2, -3, and 4 in Example 6 of the present invention (adsorption line branching, BJH method). detailed description
• the invention is characterized in that the synthesized SAPO-34 molecular sieve has a mesoporous pore size of 2-10 nm and a mesopore volume of 0.03-0.3 cm 3 /g.
• the invention is characterized in that the cubic grain surface of the synthesized SAPO-34 molecular sieve may be rough or stepped.
• the present invention is characterized in that triethylamine is used as a templating agent while a channel modifier is added to the synthetic gel.
• the method for synthesizing SAPO-34 molecular sieve with microporous mesoporous structure provided by the invention is as follows: a) preparing an initial gel mixture of synthetic SAPO-34 molecular sieve, the molar ratio of each component oxide is
• Si0 2 /Al 2 0 3 0.1-2.0;
• the channel modifier is a mixture of one or more of ammonia, tetramethylammonium hydroxide, diethylamine, tripropylamine, di-n-propylamine, n-propylamine, n-butylamine, cyclohexylamine.
• the gel mixture obtained in step a) is placed in a stainless steel synthetic kettle lined with polytetrafluoroethylene, sealed, then heated to a crystallization temperature, and subjected to constant temperature crystallization under autogenous pressure, a crystallization temperature of 100 - 250 ° C, crystallization time 5 - 100 hours. After the crystallization is completed, the solid product is separated by centrifugation, washed with deionized water to neutrality, and dried in air at 120 ° C to obtain a raw powder of SAPO-34 molecular sieve;
• the SAPO-34 molecular sieve raw powder obtained in the step b) is calcined in the air to remove the organic matter to obtain a SAPO-34 molecular sieve having a microporous mesoporous distribution.
• the invention is described in detail below by way of examples.
• the metering materials are mixed in a certain order, and each raw material used is TEA. (Analytically pure), silica sol (Si0 2 content: 30% by weight), pseudo-Bethite (A) 2 0 3 content: 70% by weight, and phosphoric acid (H 3 P0 4 content: 85% by weight).
• the raw materials were mixed in a certain order at an initial gel molar ratio of 3.0 TEA: 0.4 SiO 2 : P 2 0 5 : Al 2 0 3 : 503 ⁇ 4 O.
• the respective materials used were TEA (analytical grade) and silica sol (Si0 2 ). Content 30 wt%), pseudo-Bismite (A1 2 0 3 content 70 wt%), phosphoric acid (H 3 P0 4 content 85 wt%).
• the mixture was thoroughly stirred to form a gel, placed in a synthetic kettle called polytetrafluoroethylene, sealed and heated to 200 ° C, and subjected to constant temperature crystallization under autogenous pressure for 12 hours.
• Example 2 The No. MSP34-1 sample obtained in Example 1 and the No.
• the mixture was thoroughly stirred to form a gel, placed in a synthetic kettle called polytetrafluoroethylene, sealed and heated to 200 ° C, and subjected to constant temperature crystallization under autogenous pressure for 12 hours.
• the solid product is separated by centrifugation, washed with deionized water to neutrality, and dried in air at 120 ° C to obtain a raw powder of SAPO-34 molecular sieve.
• the original powder is calcined at 600 ° C for 4 hours to remove the templating agent.
• SAPO-34 molecular sieve (numbered MSP34-2) with pore structure in the pores.
• the XRD spectrum of the original powder sample is shown in Fig. 1, and the SEM photograph is shown in Fig. 2. It can be seen that the cubic grain surface of the MSP34-2 sample is rough or damaged.
• TEA analytical grade
• silica sol Si0 2 content 30 wt%)
• pseudo-Bohmite A] 2 0 3 content 70 wt%)
• phosphoric acid 3 ⁇ 4 P0 4 content 85 t%).
• the mixture was thoroughly stirred to form a gel, placed in a synthetic kettle called polytetrafluoroethylene, sealed and heated to 200 ° C, and subjected to constant temperature crystallization under autogenous pressure for 12 hours.
• the samples numbered MSP34-2, -3, -4 obtained in Examples 3, 4, and 5 were characterized by nitrogen physical adsorption, and the specific surface area and pore structure of the molecular sieve were determined.
• the nitrogen adsorption isotherms and mesopores are shown in Figure 4.
• the specific surface area and pore volume are shown in Table 1.
• the results showed that there was a mesoporous distribution in the MSP34-2, -3, -4 samples, and there were two different pore sizes in the MSP34-3 sample, 2 nm and 3 nm, respectively.
• the mesopore volumes of the three samples were 0.09, 0.06, and 0.14 cm 3 /g, respectively.
• the BJH method calculates the cumulative desorption pore volume in the range of 2-50 nm.
• Example 8 A sample of No. SP34 obtained in Example 1 and designated as MSP34-1 and Comparative Example 1 was subjected to air baking at 600 ° C for 4 hours, and then tableted and crushed to 20 to 40 mesh. The l.Og sample was weighed into a fixed bed reactor for MTO reaction evaluation. The reaction was carried out by a nitrogen gas activation at 550 ° C for 1 hour and then cooling to 450 ° C. Methanol was carried by nitrogen with a nitrogen flow rate of 40 ml/min and a methanol weight space velocity of 4.01 ⁇ . Reaction product Online gas chromatography was performed for analysis. The results are shown in Table 2.
• Example 8 A sample of No. SP34 obtained in Example 1 and designated as MSP34-1 and Comparative Example 1 was subjected to air baking at 600 ° C for 4 hours, and then tableted and crushed to 20 to 40 mesh. The l.Og sample was weighed into a fixed bed reactor for MTO reaction evaluation. The reaction was carried out by a nitrogen gas activation at 550 ° C

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