WO2022052967A1 - Scm-34分子筛及其制备方法和应用 - Google Patents

Scm-34分子筛及其制备方法和应用 Download PDF

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WO2022052967A1
WO2022052967A1 PCT/CN2021/117344 CN2021117344W WO2022052967A1 WO 2022052967 A1 WO2022052967 A1 WO 2022052967A1 CN 2021117344 W CN2021117344 W CN 2021117344W WO 2022052967 A1 WO2022052967 A1 WO 2022052967A1
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molecular sieve
solvent
scm
organic
sapo
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French (fr)
Inventor
杨为民
乔健
袁志庆
王振东
滕加伟
陶伟川
付文华
刘松霖
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority claimed from CN202010962076.8A external-priority patent/CN114180597B/zh
Priority claimed from CN202110438110.6A external-priority patent/CN115231584B/zh
Priority claimed from CN202110699686.8A external-priority patent/CN115504485B/zh
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to US18/245,202 priority Critical patent/US12194446B2/en
Priority to EP21866019.9A priority patent/EP4197971B1/en
Priority to JP2023516537A priority patent/JP7728335B2/ja
Priority to KR1020237012873A priority patent/KR102961787B1/ko
Priority to BR112023003730A priority patent/BR112023003730A2/pt
Publication of WO2022052967A1 publication Critical patent/WO2022052967A1/zh
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    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
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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
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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
    • C01B39/026—After-treatment
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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
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    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the invention relates to the field of molecular sieves, in particular to an SCM-34 molecular sieve and a preparation method and application thereof.
  • Porous materials are a class of solid-state compounds with regular pore structures. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), materials with a pore size of less than 2 nm in porous materials are classified as microporous materials; when the pore size is greater than 2 nm It is classified as mesopore materials or macropore materials (with a pore size greater than 50 nm).
  • the pore diameter of molecular sieve materials is generally less than 2 nm. It is a microporous material and is a kind of porous material with selective adsorption as the main feature. , its unique channel system enables it to sieve small molecules of different sizes, and "molecular sieve" is named for this.
  • Such materials have a wide range of internal pore size distribution and rich and diverse topological structures, and are widely used in adsorption and separation, heterogeneous catalysis, support for various guest molecules, and ion exchange. Excellent technology has been achieved. Effect.
  • the traditional zeolite molecular sieve is a crystalline silicate material, generally composed of silicon-oxygen tetrahedron [SiO 4 ] 4- and aluminum-oxygen tetrahedron [AlO 4 ] 5- connected by shared oxygen atoms, collectively referred to as TO 4 tetrahedron body (primary structural unit), in which the silicon element can also be replaced by other elements, especially some trivalent or tetravalent elements such as Al, B, Ga, Ge, Ti, etc.
  • TO 4 tetrahedron body primary structural unit
  • zeolite molecular sieves are widely used in the fields of catalysis, adsorption and ion exchange.
  • a key factor that determines the application performance of molecular sieves is its channel or cage characteristics, and these characteristics are determined by the intrinsic crystal structure of molecular sieves. Therefore, obtaining molecular sieves with new crystal structures is of great significance for the development of molecular sieve applications. .
  • SAPO-n In the structure of SAPO-n, after the Si atom replaces the P or Al atom in the original AlPO, a non-neutral molecular sieve framework composed of SiO 4 , AlO 4 and PO 4 tetrahedra is formed. There are two ways: (1) one Si atom replaces one P atom; (2) two silicon atoms replace a pair of aluminum atoms and phosphorus atoms, respectively.
  • the representative SAPO-n molecular sieve is the SAPO-34 molecular sieve whose topology structure is CHA.
  • the molecular sieve framework structure is similar to chabazite and belongs to the cubic crystal system.
  • the structural unit is composed of AlO 2 - , SiO 2 and PO 2 + four sides.
  • the skeleton consists of an ellipsoidal supercages and a three-dimensional intersecting structure of 8-membered ring channels.
  • the 8-membered ring channels have a pore diameter of about 0.38 nm, and the pore diameter of the supercages is kept between 0.43 and 0.50 nm.
  • Suitable protonic acidity, large specific surface area, good adsorption performance, good thermal stability, good hydrothermal stability and excellent shape selectivity of pore structure to light olefins, SAPO-34 molecular sieve as Catalysts for methanol-to-light olefins (MTO) have been successfully commercialized and exhibit good catalytic activity and selectivity.
  • Most of the known topologically linked molecular sieves are prepared by hydrothermal or solvothermal synthesis.
  • the main steps of a typical hydrothermal or solvothermal synthesis method are to firstly uniformly mix reactants such as metal sources, non-metallic sources, organic templates, solvents, etc. to obtain an initial sol, that is, the mixture to be crystallized, and then to crystallize the mixture.
  • the mixture is placed in a reaction kettle with PTFE as the inner lining and stainless steel as the outer wall. After being sealed, the crystallization reaction is carried out at a certain temperature and autogenous pressure, just like the process of rock formation in the earth, that is, the molecular sieve crystals are precipitated from the crystallization mixture. out process.
  • the reaction mixture includes framework reactants (such as silica sol, phosphoric acid and alumina), structure directing agent (SDA) and water, mixed uniformly, and left to stand or Dynamically placed in a fixed temperature oven (160-220°C) for several days for the crystallization reaction.
  • framework reactants such as silica sol, phosphoric acid and alumina
  • SDA structure directing agent
  • water mixed uniformly, and left to stand or Dynamically placed in a fixed temperature oven (160-220°C) for several days for the crystallization reaction.
  • the solid product containing SAPO-34 molecular sieve is filtered out and dried for later use.
  • the invention provides an SCM-34 molecular sieve and a preparation method and application thereof.
  • the SCM-34 molecular sieve is a new type of molecular sieve with a new framework structure, which can be used to prepare metal-containing AFI molecular sieve or SAPO-17 molecular sieve, which meets the different requirements for catalysts in chemical production.
  • a first aspect of the present invention provides an SCM-34 molecular sieve, characterized in that the SCM-34 molecular sieve contains aluminum, phosphorus, oxygen and optionally silicon; in the XRD diffraction data of the molecular sieve, the 2 ⁇ angle is at 5- The 2 ⁇ angle of the strongest peak in the range of 50° is 7.59 ⁇ 0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the following table:
  • the present invention further provides an SCM-34 molecular sieve
  • the SCM-34 molecular sieve has a schematic chemical composition as shown in the formula "Al 2 O 3 : xSiO 2 : yP 2 O", wherein 0 ⁇ x ⁇ 0.5 , 0.75 ⁇ y ⁇ 1.5; in the XRD diffraction data of the molecular sieve, the 2 ⁇ angle of the strongest peak in the range of 5-50° is 7.59 ⁇ 0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve includes the following table X-ray diffraction peaks shown:
  • the X-ray diffraction pattern of the SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:
  • the X-ray diffraction pattern of the SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:
  • the incident ray of X-ray diffraction is Cu K ⁇ 1.
  • a second aspect of the present invention provides a method for preparing the above-mentioned SCM-34 molecular sieve, comprising: adding an aluminum source, a phosphorus source, an organic template agent R1 and an organic template agent R2, a solvent S1, a solvent S2 and a solvent S3, and an optional The mixture of the added silicon source is crystallized to obtain SCM-34 molecular sieve;
  • the organic template agent R1 is selected from one or more of quaternary ammonium salts and/or quaternary ammonium bases; the organic template agent R2 is selected from one or more of imidazole, pyrrolidine, and derivatives thereof; Solvent S1 is selected from one or more of amide-based solvents; Solvent S2 is selected from one or more of cyclic organic solvents; Solvent S3 is selected from one or more of water or low-carbon alcohols, wherein organic The templating agent R1 and the organic templating agent R2 represent organic templating agents different from each other, and the solvent S1 , the solvent S2 and the solvent S3 represent solvents different from each other.
  • the organic template agent R1 is selected from tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide One or more of;
  • the organic template R2 is selected from imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl) imidazole, 2-ethyl-4-methyl One or more of imidazole, pyrrolidine, 1-(3-pyrrolidine)pyrrolidine, N-ethyl-2-aminomethylpyrrolidine;
  • the solvent S1 is selected from N,N-dimethylmethane One or more of amide, N,N-dimethylacetamide, N,N-diethylformamide and N,N-dibutylformamide;
  • the organic template agent R1 is preferably one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide;
  • the organic template agent R2 It is preferably one or more of 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole and N-ethyl-2-aminomethylpyrrolidine;
  • the solvent S1 is preferably One or both of N,N-dimethylacetamide and N,N-dibutylformamide;
  • the solvent S2 is preferably one or both of 1,4-dioxane and cyclohexanone and/or
  • the solvent S3 is preferably one or both of ethanol and water, wherein the water is preferably deionized water.
  • the molar composition of the aluminum source is calculated as Al 2 O 3
  • the silicon source is calculated as SiO 2
  • the phosphorus source is calculated as P 2 O 5
  • the molar ratio of the organic templating agent R1 to the organic templating agent R2 is 0.01-1:1, preferably 0.1-0.25:1.
  • the molar ratio of the solvent S1, the solvent S2, and the solvent S3 is 1:0.01-1:1-100, preferably 1:0.05-0.5:10-80.
  • the aluminum source is selected from one or more of aluminum isopropoxide, aluminate, metaaluminate, aluminum salt, aluminum hydroxide, aluminum oxide and aluminum-containing minerals, preferably It is one or both of aluminate and meta-aluminate;
  • the silicon source is selected from one of organosilicon, amorphous silica, silica sol, solid silica, silica gel, diatomaceous earth and water glass one or more, preferably one or more of amorphous silica, silica sol and solid silica;
  • the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate, Orthophosphoric acid is preferred.
  • stirring and precipitation treatment are performed before the crystallization treatment.
  • the stirring time is 0.5-5 h
  • the precipitation treatment time is 1-12 h.
  • the conditions of the crystallization treatment include: the crystallization temperature is 120-200°C, preferably 140-180°C, more preferably 140-160°C; the crystallization time is 1-5 days, preferably 3-5 days days, more preferably 4 to 5 days.
  • the crystallization treatment is followed by conventional post-treatment, such as the steps of filtering, washing, and drying to obtain the molecular sieve; and optionally, the step of calcining the obtained molecular sieve.
  • a third aspect of the present invention provides a molecular sieve composition, comprising the SCM-34 molecular sieve according to the first aspect or the SCM-34 molecular sieve prepared according to the method described in the second aspect, and a binder.
  • the preparation method of this molecular sieve composition comprises the following steps:
  • step b After weighing a certain amount of hydrogen-type SCM-34 molecular sieve obtained in step a and uniformly mixing it with a certain amount of binder and pore-forming agent, then with a certain amount of water and dilute nitric acid solution, kneading and extrusion molding to obtain a column
  • the strip-shaped sample is successively dried at 80-120° C. and calcined at 500-650° C. to obtain a catalyst sample; wherein, the pore-forming agent is selected from at least one of sycamore powder, carboxymethyl cellulose and starch.
  • the fourth aspect of the present invention provides an application of a molecular sieve, that is, the SCM-34 molecular sieve according to the first aspect, the SCM-34 molecular sieve prepared according to the method described in the second aspect, or the molecular sieve according to the third aspect.
  • the SCM-34 molecular sieve composition described is used to prepare metal-containing AFI molecular sieves.
  • the metal-containing AFI molecular sieve has special acid distribution and novel morphology, and is suitable for methanol-to-olefin reaction.
  • the metal element in the metal-containing AFI molecular sieve is an alkaline earth metal and/or a transition metal element, preferably at least one metal selected from Group IIA, Group IIB, Group IIIB, Group IVB or Group VIIIB
  • the element is more preferably at least one of magnesium, zinc, lanthanum, titanium, and cobalt. Based on the mass of the AFI molecular sieve, the content of the metal element is preferably 0.01% to 1.0%.
  • the metal-containing AFI molecular sieve has a weak acid center, a medium-strong acid center and a strong acid center at the same time, and the acid content distribution is as follows: the weak acid content accounts for 30% to 50% of the total acid content, and the medium and strong acid content accounts for 5% to 20% of the total acid content. , the content of strong acid accounts for 30% to 65% of the total acid content.
  • the preparation method of the metal-containing AFI molecular sieve includes: using the SCM-34 molecular sieve of the present invention as a reactant raw material, mixing it with a solvent SI, an organic template R, and a selectively added first silicon source to prepare a precursor A, and then mixing with the solvent
  • the AFI molecular sieve is prepared by mixing SII, a metal source, and a selectively added second silicon source.
  • the mass ratio of solvent SI to solvent SII is 0.1-20:1.
  • preparation method of described AFI molecular sieve specifically comprises the following steps:
  • step c The mixture to be crystallized in step c is placed under the condition of 60-100° C. and continues to be stirred for 0.5-2 h, and then crystallization reaction is carried out to obtain AFI molecular sieve.
  • the organic template agent R is an organic amine
  • the organic amine is preferably selected from tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium ammonium bromide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltrimethylammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine At least one of them is more preferably at least one of tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide and triethylamine.
  • solvent SI or solvent SII is independently selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol, ethanol and water, preferably N , at least one of N-dimethylformamide, ethanol and water.
  • first silicon source or the second silicon source is independently selected from at least one of organic silicon, amorphous silica, silica sol and solid silica; preferably amorphous silica, silica sol and at least one of solid silica.
  • the metal source is selected from at least one of nitrates, sulfates and acetates of corresponding alkaline earth metals and/or transition metal elements, preferably nitrates of corresponding metals.
  • step a the heat treatment conditions are: treatment at 40-80° C. for 0.5-2 hours.
  • the conditions of the crystallization reaction are: 110-160°C, preferably 110-145°C, more preferably 120-135°C; the reaction time range is 10-120 minutes, preferably 20-100°C minutes, more preferably 30 to 90 minutes.
  • step d the crystallized product can be subjected to post-processing steps, such as filtration, washing, drying, roasting, etc., and the post-processing steps can adopt conventional operating conditions in the art.
  • post-processing steps such as filtration, washing, drying, roasting, etc.
  • the obtained product mixture can be simply filtered with suction.
  • the washing include washing with deionized water and/or ethanol.
  • the drying temperature is, for example, 40 to 250° C., preferably 60 to 150° C.
  • the drying time is, for example, 3 to 30 hours, preferably 5 to 20 hours. This drying may be performed under normal pressure or under reduced pressure.
  • the calcination can be performed in any manner conventionally known in the art.
  • the calcination temperature is generally 300-800° C., preferably 400-650° C.
  • the calcination time is generally 1-12 hours, preferably 3-12 hours.
  • the firing is generally carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere.
  • the metal-containing AFI molecular sieve can be used in the reaction of methanol to hydrocarbons.
  • the reaction conditions for preparing hydrocarbons from methanol are as follows: using methanol as a raw material, the reaction temperature is 400-600° C., the reaction pressure is 0.01-10 MPa, and the methanol weight space velocity is 0.1-15 h ⁇ 1 .
  • the preparation method of the AFI molecular sieve of the present invention can be rapidly crystallized at a relatively low temperature.
  • the minimum reaction temperature is 110° C. and the fastest reaction time is 10 minutes.
  • the obtained AFI molecular sieve is suitable for the reaction of methanol to olefin, and has achieved good technical effect.
  • a fifth aspect of the present invention provides an application of a molecular sieve, according to the SCM-34 molecular sieve described in the first aspect, the SCM-34 molecular sieve prepared according to the method described in the second aspect, or the SCM-34 molecular sieve described in the third aspect.
  • the SCM-34 molecular sieve composition was used to prepare the SAPO-17 molecular sieve.
  • the SAPO-17 molecular sieve prepared here can be used for industrial production of methanol downstream products, industrial production of syngas downstream products and hydrocarbon cracking, and has excellent performance.
  • the preparation method of the SAPO-17 molecular sieve comprises the following steps:
  • step 4) The mixture to be crystallized obtained in step 3) is pretreated, and then subjected to a crystallization reaction to obtain SAPO-17 molecular sieve.
  • the organic template cR is at least one of 1,10-o-phenanthroline, 2,2-bipyridine, 4,4-bipyridine, piperazine, cyclohexylamine, and pyridine species; preferably at least one of piperazine and cyclohexylamine.
  • the first organic solvent cS and the second organic solvent cS are independently selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-epoxycyclopentane, 1, At least one of 4-dioxane, cyclohexanone and cyclohexanol; preferably at least one of 1, 4-dioxane and cyclohexanone.
  • the mass ratio of the added SCM-34 molecular sieve to the organic template agent cR and all the organic solvents cS is 0.1-1:1-10:1-10.
  • the total organic solvent is the total amount of the first organic solvent cS described in step 1) and the second organic solvent cS described in step 2).
  • the mass ratio of the first organic solvent cS in step 1) to the second organic solvent cS in step 2) is 1:0.1-1.
  • the temperature of the first heat treatment is 40-90°C, and the time is 1-5h; preferably, the temperature of the first heat treatment is 55-75°C, and the time is 2-4h.
  • the temperature of the second heat treatment is 40-90°C, and the time is 1-5h; preferably, the temperature of the second heat treatment is 50-70°C, and the time is 2-3h.
  • the mass ratio of the silicon source to the SCM-34 molecular sieve is: 0-10:1, preferably 0.1-10:1.
  • the silicon source is at least one of organic silicon, amorphous silicon dioxide, silica sol, white carbon black, silica gel, diatomaceous earth and water glass; preferably amorphous silicon dioxide , at least one of silica sol and silica.
  • step 3 the mixing is preferably by adding the precursor P to the mixed material M under stirring, and the stirring time is 0.5-5 h, preferably 2.5-4 h.
  • step 4 the conditions of the pretreatment are: stirring at 80-110° C. for 0.5-5 h.
  • step 4 the conditions of the crystallization reaction are: crystallization at 115-140° C. for 1-8 hours.
  • the SAPO-17 molecular sieve can be used in the reaction of methanol to hydrocarbons and the reaction of synthesis gas to olefins.
  • reaction conditions for preparing hydrocarbons from methanol are as follows: using methanol as a raw material, the reaction temperature is 400-600° C., the reaction pressure is 0.01-10 MPa, and the methanol weight space velocity is 0.1-15 h ⁇ 1 .
  • the SAPO-17 molecular sieve prepared by the invention When the SAPO-17 molecular sieve prepared by the invention is applied to the reaction of methanol to hydrocarbons, within the set evaluation condition range, the methanol conversion rate is 100%, the single-pass yield of ethylene and propylene can reach up to 84.5%, and the selectivity When the ratio (ethylene/propylene) is in the range of 2.5 to 3.0, the catalyst has good stability.
  • the SAPO-17 molecular sieve prepared by the invention is applied to the reaction process of synthesis gas to olefin.
  • the CO conversion rate can reach up to 51.7%
  • the selectivity of C 2 -C 4 olefin can reach up to 85.6%.
  • the selectivity ratio (ethylene/propylene) is in the range of 2.5 to 3.0.
  • the crystallization time for preparing the SAPO-17 molecular sieve by the method of the present invention is shorter, and at the same time, the total synthesis time of the SAPO-17 molecular sieve can be shortened to a certain extent, and can be carried out at a lower temperature.
  • the SAPO-17 molecular sieve prepared by crystallizing the SCM-34 molecular sieve of the present invention significantly improves the performance of the SAPO-17 molecular sieve.
  • the SAPO-17 molecular sieve synthesized by this method shows excellent performance when it is used in the industrial production of methanol downstream products, the industrial production of syngas downstream products and hydrocarbon cracking, such as in the reaction of methanol conversion to hydrocarbons, ethylene and propylene
  • the total yield is high, and the selectivity ratio (ethylene/propylene) is high, and in the synthesis gas to hydrocarbon reaction, the selectivity of C2 - C4 olefins is high, and the selectivity ratio (ethylene/propylene) is high.
  • Fig. 1 is the X-ray diffraction (XRD) pattern of the molecular sieve prepared in Example 1;
  • Fig. 2 is the SEM photograph of the molecular sieve prepared in Example 1;
  • Fig. 3 is the XRD pattern of the AFI molecular sieve synthesized in Example 9;
  • Fig. 4, Fig. 5 are the SEM photos of the AFI molecular sieve synthesized in Example 9;
  • Example 6 is a TPD diagram of the AFI molecular sieve synthesized in Example 9.
  • Fig. 7 is the XRD pattern of the SAPO-17 molecular sieve of embodiment 13;
  • Fig. 8 is the SEM photograph of the SAPO-17 molecular sieve of Example 13;
  • Fig. 9 is the XRD pattern of the SAPO-17 molecular sieve of comparative example 1;
  • XRD X-ray diffraction pattern
  • the X'Pert PRO X-ray powder diffraction (XRD) instrument of the Netherlands PANalytical Company is adopted, the working voltage is 40kV, the current is 40mA, and the scanning range is 3.5-50°.
  • the morphology of the product was photographed by S-4800 Field Emission Scanning Electron Microscope (Fe-SEM) from HITACHI Company of Japan.
  • Phosphoric acid (purity ⁇ 85wt.%): containing P 2 O 5 , 72.3 wt %, commercial product;
  • Acidic silica sol (40 wt. % aqueous solution): containing SiO 2 , 40 wt %, commercially available;
  • Cobalt nitrate [Co(NO 3 ) 2 ⁇ 6H 2 O]: containing CoO, 25.7% by weight;
  • Al(iPr) 3 aluminum isopropoxide
  • the precursor P 2 was put into the mixture M 2 under vigorous stirring, and after stirring for 4.0 hours, it was placed at 80°C for 5 hours of airtight stirring; it was then crystallized at 130°C for 2 hours.
  • the product was filtered, washed, and dried at 100°C for 6 hours, and then The temperature was raised to 600°C, and the product was obtained by constant temperature calcination for 4h, which was denoted as STE-2.
  • Its XRD pattern is similar to that of FIG. 7
  • its SEM image is similar to that of FIG. 8 .
  • HCHA cyclohexylamine
  • PIP piperazine
  • DOA 1,4-dioxane
  • CHO cyclohexanone
  • the precursor P 3 was put into the mixture M 3 under vigorous stirring, and after stirring for 1 hour, it was placed at 100°C for 1 hour of airtight stirring; then placed at 120°C for 5 hours of crystallization, the product was filtered and washed, dried at 80°C for 9 hours, and then heated up To 400 °C, constant temperature calcination for 8h to obtain the product, denoted as STE-3.
  • Its XRD pattern is similar to that of FIG. 7
  • its SEM image is similar to that of FIG. 8 .
  • the preparation of SAPO-17 molecular sieve is as follows: using aluminum isopropoxide as the aluminum source, phosphoric acid as the phosphorus source, silica sol as the silicon source, and cyclohexylamine as the template agent, 81 g of The aluminum isopropoxide was added to 48.9 g of ultrapure water, stirred evenly, and then added 45.7 g of phosphoric acid (85 wt.%).
  • silica sol 40 wt.% was added to the reaction system, and after stirring for several hours, the sol was placed in a stainless steel reaction kettle containing PTFE lining and crystallized at 200 °C for 120 h to obtain SAPO -17 molecular sieve.
  • the STE-1 molecular sieve synthesized in Example 13 was taken, calcined at 550° C. for 4 hours, cooled to room temperature, compressed, crushed and sieved, and 12-20 mesh granules were taken for later use.
  • Example 15 Take the STE-3 molecular sieve synthesized in Example 15, and use the catalyst preparation method in Example 16 to prepare a catalyst.
  • ZnCrO x represents the mixture of zinc oxide and chromium oxide, and the oxide-molecular sieve catalyst is prepared for use).
  • reaction temperature 400 ° C reaction temperature 400 ° C
  • pressure 10 MPa space velocity 2000 h -1
  • Example 14 Take the STE-2 molecular sieve synthesized in Example 14, and use the catalyst preparation method in Example 19 to prepare a catalyst.
  • Example 15 Take the STE-3 molecular sieve synthesized in Example 15, and use the catalyst preparation method in Example 19 to prepare a catalyst.

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Abstract

本发明公开了一种SCM-34分子筛及其制备方法和应用。所述SCM-34分子筛包含铝，磷，氧和任选的硅，其中所述分子筛的XRD衍射数据中，2θ角在5-50°范围内最强峰的2θ角为7.59±0.2。该SCM-34分子筛具有新的骨架结构，可以用于制备含金属的AFI分子筛或SAPO-17分子筛，满足了化工生产中对于催化剂的不同需求。

Description

SCM-34分子筛及其制备方法和应用 技术领域
本发明涉及分子筛领域，具体涉及一种SCM-34分子筛及其制备方法和应用。
背景技术
多孔材料是一类具有规则孔结构的固态化合物，按照国际纯粹和应用化学联合会(IUPAC)的定义，多孔材料中孔径小于2nm的材料归属为微孔材料(micropore materials)；孔径在2nm以上时归属为介孔材料(mesopore materials)或大孔材料(macropore materials，孔径大于50nm)，分子筛材料的孔道直径一般在2nm以下，属微孔材料，是一类以选择性吸附为主要特征的多孔材料，其独特的孔道体系使其具有筛分不同尺寸小分子的能力，“分子筛”正是得名于此。且该类材料内部孔腔尺寸分布范围广和拓扑学结构的丰富多样，被广泛地应用在吸附分离、非均相催化、各类客体分子的载体和离子交换等领域，取得了极好的技术效果。
传统的沸石分子筛为一种结晶的硅酸盐材料，一般由硅氧四面体[SiO 4] 4-和铝氧四面体[AlO 4] 5-通过共用氧原子连接而成，统称为TO 4四面体(初级结构单元)，其中的硅元素也可以被其它元素，特别是一些三价或四价元素如Al、B、Ga、Ge、Ti等部分同晶取代，由于其结构和化学性质上的一些特殊性，沸石分子筛在催化、吸附以及离子交换等领域都具有广泛应用。决定分子筛应用性能的一个关键因素是其孔道或者笼穴特征，而这些特征是由分子筛的本征晶体结构所决定的，因而获得新晶体结构的分子筛对于开拓分子筛的应用来说具有非常重要的意义。
1982年，美国联合碳化公司(UCC公司)的科学家S.T.Wilson与E.M.Flanigen等使用铝源、磷源以及有机模板剂成功的合成与开发出了一个全新的分子筛家族——磷酸铝分子筛AlPO 4-n，n代表型号(US 4310440)。两年以后，UCC公司在AlPO 4-n的基础上，使用Si原子部分替代AlPO骨架中的Al原子和P原子，成功的制备出了另一系列磷酸硅铝分子筛：SAPO-n，n代表型号。在SAPO-n的结构中， Si原子代替原AlPO中的P或Al原子后，形成由SiO 4、AlO 4以及PO 4四面体组成的非中性分子筛骨架，在这类分子筛的骨架中硅以两种方式存在：(1)一个Si原子取代一个P原子；(2)2个硅原子分别取代一对铝原子和磷原子。比较具有代表性的SAPO-n分子筛为拓扑学结构是CHA的SAPO-34分子筛，该分子筛骨架结构类似菱沸石，属于立方晶系，结构基元是由AlO 2 -、SiO 2以及PO 2 +四面体组成，骨架中包含有椭球形超笼以及8-元环孔道的三维交叉结构，其8-元环孔道孔径约为0.38nm，超笼的孔口直径保持在0.43～0.50nm之间因具有适合的质子酸性、较大的比表面积、较好的吸附性能、较好的热稳定性、良好的水热稳定性以及孔道结构对低碳烯烃的择形选择性极佳，SAPO-34分子筛作为甲醇制低碳烯烃(MTO)的催化剂已成功地进行商业化应用，并表现出了很好的催化活性以及选择性。
目前已知拓扑学结钩的分子筛大多是采用水热或溶剂热合成的方法被制备出来的。一个典型的水热或溶剂热合成法的主要步骤是首先将金属源、非金属源、有机模板剂、溶剂等反应物均匀混合，得到初始溶胶即待晶化混合物，然后再将该待晶化混合物置于聚四氟乙烯为内衬、不锈钢为外壁的反应釜中，密闭后在一定的温度和自生压力下进行晶化反应，如同地球造岩的过程，即分子筛晶体从晶化混合物中沉淀出来的过程。具体以合成硅磷铝类SAPO-34分子筛举例来说，所述反应混合物包含骨架反应物(例如二氧化硅溶胶、磷酸和氧化铝)和结构导向剂(SDA)和水混合均匀，静置或动态放置于固定温度的烘箱(160-220℃)数天，用以进行晶化反应。当晶化反应完成时，过滤出含有SAPO-34分子筛的固体产物，烘干备用。
截止目前(2021年8月4日)，据国际分子筛协会显示，包括最新具有ANO拓扑学结构的AlPO-91分子筛[US Patent 10336,622 B1，，(2019)，Crystalline metallophosphates，their method of preparation，and use，Yuhas，B.D.，Wilson，K.N.，Sylejmani-Rekaliu，M.，Mowat，J.P.S.，Sinkler，W.]在内，总计已有255种拓扑学结构不同的分子筛，虽然已经获得了诸多不同的结晶分子筛，但开发具有用于气体分离和干燥、烃转化反应和其它应用的期望性质的新型分子筛仍是目前研究的热点。
发明内容
本发明提供一种SCM-34分子筛及其制备方法和应用。该SCM-34分子筛是一种新型分子筛，具有新的骨架结构，可以用于制备含金属的AFI分子筛或SAPO-17分子筛，满足了化工生产中对于催化剂的不同需求。
本发明第一方面提供了一种SCM-34分子筛，其特征在于，所述SCM-34分子筛包含铝，磷，氧和任选的硅；所述分子筛的XRD衍射数据中，2θ角在5-50°范围内最强峰的2θ角为7.59±0.2；所述SCM-34分子筛的X射线衍射图谱包括如下表所示的X射线衍射峰：
2θ(°) 相对强度，[(I/I 0)×100]
7.59±0.2 100
10.81±0.1 5-50
16.52±0.1 5-50
17.97±0.1 5-50
23.34±0.05 5-50
。
本发明进一步地提供了一种SCM-34分子筛，所述SCM-34分子筛具有如式“Al 2O 3：xSiO 2：yP 2O”所示的示意性化学组成，其中，0≤x≤0.5，0.75≤y≤1.5；所述分子筛的XRD衍射数据中，2θ角在5-50°范围内最强峰的2θ角为7.59±0.2；所述SCM-34分子筛的X射线衍射图谱包括如下表所示的X射线衍射峰：
2θ(°) 相对强度，[(I/I 0)×100]
7.59±0.2 100
10.81±0.1 5-50
16.52±0.1 5-50
17.97±0.1 5-50
23.34±0.05 5-50
34.74±0.05 5-50
。
进一步地，所述SCM-34分子筛的X射线衍射图谱还包括如下表所示的X射线衍射峰：
2θ(°) 相对强度，[(I/I 0)×100]
14.25±0.1 5-50
21.01±0.1 10-20
24.27±0.05 5-50
26.05±0.05 5-50
27.82±0.05 5-50
28.15±0.02 5-50
30.03±0.02 5-50
。
进一步地，所述SCM-34分子筛的X射线衍射图谱还包括如下表所示的X射线衍射峰：
2θ(°) 相对强度，[(I/I 0)×100]
10.33±0.1 10-20
12.09±0.1 5-50
19.77±0.1 5-50
31.33±0.01 5-50
38.29±0.01 5-50
。
其中，X射线衍射的入射线为Cu Kα1。
本发明第二方面提供了一种上述SCM-34分子筛的制备方法，包括：将含有铝源、磷源、有机模板剂R1和有机模板剂R2、溶剂S1、溶剂S2和溶剂S3、和任选加入的硅源的混合物进行晶化处理，得到SCM-34分子筛；
其中，所述有机模板剂R1选自季铵盐和/或季铵碱中的一种或几种；有机模板剂R2选自咪唑，吡咯烷，和其衍生物中的一种或几种；溶剂S1选自酰胺基溶剂中的一种或几种；溶剂S2选自环状有机溶剂中的一种或几种；溶剂S3选自水或低碳醇中的一种或几种，其中有机模板剂R1和有机模板剂R2代表彼此不同的有机模板剂，以及溶剂S1、溶剂S2和溶剂S3代表彼此不同的溶剂。
进一步地，所述有机模板剂R1选自四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、四丙基氢氧化铵、四丁基溴化铵、四丁基氢氧化 铵中的一种或几种；所述有机模板剂R2选自咪唑、2-甲基咪唑、4-甲基咪唑、1-(3-氨基丙基)咪唑、2-乙基-4-甲基咪唑、吡咯烷、1-(3-吡咯烷)吡咯烷、N-乙基-2-氨甲基吡咯烷中的一种或几种；所述溶剂S1选自N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N，N-二乙基甲酰胺和N，N-二丁基甲酰胺中的一种或几种；所述溶剂S2选自1，4-二氧六环、环己烷、环己酮和环己醇中的一种或几种；和/或所述溶剂S3选自甲醇、乙醇、乙二醇、丁醇和水中的一种或多种。
进一步地，所述有机模板剂R1优选为四乙基溴化铵、四乙基氢氧化铵、四丙基氢氧化铵和四丁基氢氧化铵中的一种或几种；所述有机模板剂R2优选为1-(3-氨基丙基)咪唑、2-乙基-4-甲基咪唑、N-乙基-2-氨甲基吡咯烷中的一种或几种；所述溶剂S1优选为N，N-二甲基乙酰胺和N，N-二丁基甲酰胺中的一种或两种；所述溶剂S2优选为1，4-二氧六环和环己酮中的一种或两种；和/或所述溶剂S3优选为乙醇和水中的一种或两种，其中水优选去离子水。
进一步地，所述混合物中，铝源以Al 2O 3计、硅源以SiO 2计、磷源以P 2O 5计、有机模板剂R1+R2、溶剂S1+S2+S3的摩尔组成如下：SiO 2/Al 2O 3＝0～1，优选为0.1～0.75；P 2O 5/Al 2O 3＝0.5～2，优选为0.75～1.5；模板剂R1+R2/Al 2O 3＝1～200，优选为5～50；溶剂S1+S2+S3/Al 2O 3＝5～500，优选为35～120。
进一步地，所述有机模板剂R1与有机模板剂R2的摩尔比为0.01～1∶1，优选为0.1～0.25∶1。
进一步地，所述溶剂S1、溶剂S2、与溶剂S3的摩尔比为1∶0.01～1∶1～100，优选为1∶0.05～0.5∶10～80。
进一步地，所述铝源选自异丙醇铝、铝酸盐、偏铝酸盐、铝盐、铝的氢氧化物、铝的氧化物和含铝的矿物中的一种或几种，优选为铝酸盐和偏铝酸盐中的一种或两种；所述硅源选自有机硅、无定形二氧化硅、硅溶胶、固体氧化硅、硅胶、硅藻土和水玻璃中的一种或几种，优选为无定形二氧化硅、硅溶胶和固体氧化硅中的一种或几种；所述磷源选自磷酸、磷酸一氢铵和磷酸二氢铵中的至少一种，优选为正磷酸。
进一步地，所述制备方法中，在进行晶化处理前，先进行搅拌、沉化处理。所述搅拌的时间为0.5～5h，所述沉化处理的时间为1～12h。
进一步地，所述晶化处理的条件包括：晶化温度为120～200℃，优选为140～180℃，更优选为140～160℃；晶化时间为1～5天，优选为3～5天，更优选为4～5天。
进一步地，所述晶化处理后进行常规的后处理，如过滤、洗涤、干燥制得所述分子筛的步骤；和任选地，焙烧所述获得的分子筛的步骤。
本发明第三方面提供了一种分子筛组合物，包括按照前述第一方面所述的SCM-34分子筛或者按照前述第二方面所述的方法制备的SCM-34分子筛，以及粘结剂。例如，该分子筛组合物的制备方法包含如下的步骤：
a.对本发明的SCM-34分子筛进行铵交换、焙烧，得到氢型SCM-34分子筛；
b.称取一定量步骤a所得的氢型SCM-34分子筛与一定量的粘结剂、造孔剂均匀混合之后，然后用一定量的水和稀硝酸溶液，混捏、挤条成型，得到柱条状样品，先后经80～120℃干燥，500～650℃焙烧，得到催化剂样品；其中，造孔剂选自田菁粉、羧甲基纤维素和淀粉中的至少一种。
本发明第四方面提供了一种分子筛的应用，即按照前述第一方面所述的SCM-34分子筛、按照前述第二方面所述的方法制备的SCM-34分子筛、或者按照前述第三方面所述的SCM-34分子筛组合物用于制备含金属的AFI分子筛。该含金属的AFI分子筛具有特殊的酸分布，且具有新型形貌，适用于甲醇制烯烃反应中。
该含金属的AFI分子筛中的金属元素为碱土金属和/或过渡金属元素，优选选自第II A族、第II B族、第IIIB族、第IVB族或第VIIIB族中的至少一种金属元素，进一步优选为镁、锌、镧、钛、钴中的至少一种。以该AFI分子筛的质量为基准，金属元素的含量优选为0.01％～1.0％。
该含金属的AFI分子筛同时具备弱酸中心、中强酸中心和强酸中心，酸量分布情况如下：弱酸含量占总酸量的30％～50％，中强酸含量占总酸量的5％～20％，强酸含量占总酸量的30％～65％。
该含金属的AFI分子筛的制备方法包括：采用本发明的SCM-34分子筛作为反应物原料，与溶剂SI、有机模板剂R、选择性加入的第 一硅源混合制备前驱体A，然后与溶剂SII、金属源、选择性加入的第二硅源混合，制备得到所述AFI分子筛。
进一步地，以投料的SCM-34分子筛的质量m为基准，所用原料的投料质量比为：硅源/m＝0～20，有机模板剂R/m＝1～20，金属源/m＝0.01～1，溶剂(SI+SII)/m＝2～100；优选为硅源/m＝0.1～10，有机模板剂R/m＝2～10，金属源/m＝0.05～0.5，溶剂(SI+SII)/m＝10～50；更优选为：硅源/m＝0.5～1，有机模板剂R/m＝3～6，金属源/m＝0.1～0.25，溶剂(SI+SII)/m＝20～40。
进一步地，溶剂SI与溶剂SII的质量比为0.1～20∶1。
进一步地，所述AFI分子筛的制备方法具体包括以下步骤：
a、将SCM-34分子筛、有机模板剂R加入到溶剂SI中，并选择性加入第一硅源，搅拌，热处理，得到前驱体A；
b、将金属源与溶剂SII混合，并选择性加入第二硅源，得到混合物B；
c、将前驱体A在搅拌状态下加入到混合物B中，形成待晶化混合物；
d、将步骤c的待晶化混合物置于60～100℃条件下继续搅拌0.5～2h后，进行晶化反应，得到AFI分子筛。
进一步地，所述有机模板剂R为有机胺，所述有机胺优选选自四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、四丙基氢氧化铵、四丁基溴化铵、四丁基氢氧化铵、苄基三乙基氯化铵、苄基三甲基氢氧化铵、三乙胺、正丁胺、二正丙胺、二异丙胺、乙二胺和乙胺中的至少一种，进一步优选为四乙基氢氧化铵、苄基三甲基氢氧化铵和三乙胺中的至少一种。
进一步地，所述溶剂SI或溶剂SII各自独立地选自N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙二醇、乙醇和水中的至少一种，优选为N，N-二甲基甲酰胺、乙醇和水中的至少一种。
进一步地，所述第一硅源或第二硅源各自独立地选自有机硅、无定形二氧化硅、硅溶胶和固体氧化硅中的至少一种；优选为无定形二氧化硅、硅溶胶和固体氧化硅中的至少一种。
进一步地，所述金属源选自相应碱土金属和/或过渡金属元素的硝酸盐、硫酸盐、醋酸盐中的至少一种，优选为相应金属的硝酸盐。
进一步地，步骤a中，所述热处理条件为：在40～80℃条件下处理0.5～2h。
进一步地，步骤d中，所述晶化反应的条件为：110～160℃，优选为110～145℃，更优选为120～135℃；反应时间范围为10～120分钟，优选为20～100分钟，更优选为30～90分钟。
进一步地，步骤d中，晶化产物可以经过后处理步骤，如过滤、洗涤、干燥、焙烧等，后处理步骤可采用本领域的常规操作条件。
具体举例而言，作为所述过滤，比如可以简单地抽滤所述获得的产物混合物。作为所述洗涤，比如可以举出使用去离子水和/或乙醇进行洗涤。作为所述干燥温度，比如可以举出40～250℃，优选60～150℃，作为所述干燥的时间，比如可以举出3～30小时，优选5～20小时。该干燥可以在常压下进行，也可以在减压下进行。所述焙烧可以按照本领域常规已知的任何方式进行，比如焙烧温度一般为300～800℃，优选400～650℃，而焙烧时间一般为1～12小时，优选3～12小时。另外，所述焙烧一般在含氧气氛下进行，比如空气或者氧气气氛下。
所述的含金属的AFI分子筛可以在甲醇制烃类反应中应用。进一步地，所述甲醇制烃类的反应条件为：以甲醇为原料，反应温度为400～600℃，反应压力为0.01～10MPa，甲醇重量空速为0.1～15h -1。
本发明AFI型分子筛的制备方法可在较低温度下快速晶化，如最低反应温度为110℃，最快反应时间为10分钟，所得AFI分子筛适用于甲醇制烯烃反应中，取得了较好的技术效果。
本发明第五方面提供了一种分子筛的应用，按照前述第一方面所述的SCM-34分子筛、按照前述第二方面所述的方法制备的SCM-34分子筛、或者按照前述第三方面所述的SCM-34分子筛组合物用于制备SAPO-17分子筛。这里制备的SAPO-17分子筛可用于甲醇下游产品的工业生产、合成气下游产品的工业生产及烃类裂解时，具有优异的性能。
在一种实施方式中，所述SAPO-17分子筛的制备方法包括如下步骤：
1)将有机模板剂cR及第一有机溶剂cS混合，进行第一热处理，得到前驱体P；
2)将本发明的SCM-34分子筛、选择性加入的硅源与第二有机溶 剂cS混合，进行第二热处理，得到混合物料M；
3)将步骤1)所得前驱体P与步骤2)所得混合物料M混合，形成待晶化混合物；
4)将步骤3)得到的待晶化混合物进行预处理，然后进行晶化反应，得到SAPO-17分子筛。
进一步地，步骤1)中，所述有机模板剂cR为1，10-邻菲罗啉、2，2-联吡啶、4，4-联吡啶、哌嗪、环己胺、吡啶中的至少一种；优选为哌嗪、环己胺中的至少一种。
进一步地，步骤1)和步骤2)中，第一有机溶剂cS和和第二有机溶剂cS各自独立地选自为四氢呋喃、2-甲基四氢呋喃、1，2-环氧环戊烷、1、4-二氧六环、环己酮、环己醇中的至少一种；优选为1、4-二氧六环、环己酮中的至少一种。
进一步地，加入的SCM-34分子筛与有机模板剂cR及全部有机溶剂cS的质量比为0.1～1∶1～10∶1～10。其中，全部有机溶剂为步骤1)中所述第一有机溶剂cS与步骤2)中所述第二有机溶剂cS的总量。步骤1)中所述第一有机溶剂cS与步骤2)中所述第二有机溶剂cS的质量比为1∶0.1～1。
进一步地，步骤1)中，所述第一热处理的温度为40～90℃，时间为1～5h；优选为所述第一热处理的温度为55～75℃，时间为2～4h。
进一步地，步骤2)中，所述第二热处理的温度为40～90℃，时间为1～5h；优选为所述第二热处理的温度为50～70℃，时间为2～3h。
进一步地，步骤2)中，所述硅源与SCM-34分子筛的质量比为：0～10∶1，优选为0.1～10∶1。
进一步地，步骤2)中，所述硅源为有机硅、无定形二氧化硅、硅溶胶、白炭黑、硅胶、硅藻土和水玻璃中的至少一种；优选为无定形二氧化硅、硅溶胶和白炭黑中的至少一种。
进一步地，步骤3)中，所述混合优选是将前驱体P在搅拌状态下加入混合物料M，所述搅拌的时间为0.5～5h，优选为2.5～4h。
进一步地，步骤4)中，所述预处理的条件为：在80～110℃下搅拌0.5～5h。
进一步地，步骤4)中，所述晶化反应的条件为：在115～140℃下晶化1～8h。
所述SAPO-17分子筛可应用于甲醇制烃类的反应、合成气制烯烃的反应中。
进一步地，甲醇制烃类的反应条件为：以甲醇为原料，反应温度为400～600℃，反应压力为0.01～10MPa，甲醇重量空速为0.1～15h -1。
进一步地，合成气制烯烃反应条件为：以合成气为原料H 2/CO＝0.5～1∶1，反应温度为200～400℃，反应压力为0.1～10MPa，合成气重量空速为20～2000h -1。
本发明制备的SAPO-17分子筛应用于甲醇制烃类的反应时，在设定的评价条件范围内，甲醇转化率为100％，乙烯、丙烯的单程收率最高可达84.5％，且选择性比率(乙烯/丙烯)在2.5～3.0范围内，催化剂具有良好的稳定性。
本发明制备的SAPO-17分子筛应用于合成气制烯烃的反应过程，在设定的评价条件范围内，CO转化率最高可达51.7％，C 2-C 4烯烃的选择性最高可达85.6％，选择性比率(乙烯/丙烯)在2.5～3.0范围内。
与现有技术相比，本发明方法制备SAPO-17分子筛的晶化时间较短，同时也能一定程度缩短SAPO-17分子筛总的合成时间，且可以在较低温度下进行。由本发明SCM-34分子筛转晶来制备的SAPO-17分子筛，显著提高了SAPO-17分子筛的使用性能。该方法合成的SAPO-17分子筛用于甲醇下游产品的工业生产、合成气下游产品的工业生产及烃类裂解时，表现出优异的性能，如用于甲醇转化制烃反应中，乙烯、丙烯的总收率高，且选择性比率(乙烯/丙烯)高，用于合成气制烃类反应中，C 2-C 4烯烃的选择性高，选择性比率(乙烯/丙烯)高。
附图说明
图1为实施例1所制备的分子筛的X射线衍射(XRD)图；
图2为实施例1所制备的分子筛的SEM照片；
图3为实施例9合成的AFI分子筛的XRD图；
图4、图5为实施例9合成的AFI分子筛的SEM照片；
图6为实施例9合成的AFI分子筛的TPD图。
图7为实施例13的SAPO-17分子筛的XRD图；
图8为实施例13的SAPO-17分子筛的SEM照片；
图9为对比例1的SAPO-17分子筛的XRD图；
图10为对比例1的SAPO-17分子筛的SEM照片。
具体实施方式
为了便于理解本发明，本发明列举如下实施例。但是本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应该视为对本发明的具体限制。在本发明中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。
在本发明中，分子筛的结构是由X-射线衍射谱图(XRD)确定的，所述分子筛的X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定，使用Cu-Kα射线源，Kα1波长λ＝1.5405980埃
Figure PCTCN2021117344-appb-000001
镍滤光片。
本发明中，采用的是荷兰帕纳科公司X’Pert PRO型X射线粉末衍射(XRD)仪，工作电压40kV，电流40mA，扫描范围3.5～50°。产物形貌采用日本HITACHI公司的S-4800型场发射扫描电镜(Fe-SEM)进行拍摄。
需要特别说明的是，在本说明书的上下文中公开的两个或多个方面(或实施方式)可以彼此任意组合，由此而形成的技术方案(比如方法或系统)属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围之内。
在没有明确指明的情况下，本发明中所提到的所有百分数、份数、比率等都是以重量为基准的，除非以重量为基准时不符合本领域技术人员的常规认识。
本发明具体实施方式中涉及的原料如下：
硫酸铝[Al 2(SO 4) 3·18H 2O]：含Al 2O 3，15.7重量％，工业品；
异丙醇铝[Al(iPr) 3]：含Al 2O 3，24.9重量％；
硝酸铝[Al(NO 3) 3·9H 2O]：含Al 2O 3，27.5重量％；
磷酸(纯度≥85wt.％)：含P 2O 5，72.3重量％，市售品；
酸性硅溶胶(40wt.％水溶液)：含SiO 2，40重量％，市售品；
白炭黑：含SiO 2，99重量％；
硝酸镁[Mg(NO 3) 2·6H 2O]：含MgO，15.6重量％；
硝酸钴[Co(NO 3) 2·6H 2O]：含CoO，25.7重量％；
硝酸锌[Zn(NO 3) 2·6H 2O]：含ZnO，27.3重量％。
一、SCM-34分子筛的制备
【实施例1】
取3.8g的硝酸铝[Al(NO 3) 3·9H 2O]溶于4.3mL去离子水中，混合形成溶液C，之后将1.8g的磷酸(纯度≥85wt.％)、10.8g的四丁基氢氧化铵(40wt.％水溶液，MkSeal)以及10.4g的1-(3-氨基丙基)咪唑加入溶液C中，搅拌0.5h、沉化12h后得溶液C’，之后向C’溶液缓慢投入0.1g的白炭黑(阿拉丁，S104573，≥99％)、1.4mL的N，N-二丁基甲酰胺以及0.4mL的环己酮，搅拌3.5h后置于90℃下热处理8h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、总模板剂和总溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶模板剂R∶溶剂S＝1∶0.1∶1.5∶5∶35，模板剂R1(四丁基氢氧化铵)/模板剂R2(1-(3-氨基丙基)咪唑)＝0.2，溶剂S1(N，N-二丁基甲酰胺)/溶剂S2(环己酮)/溶剂S3(水)＝1∶0.5∶78.5；将上述待晶化混合物置于140℃晶化5天，产物经过滤、洗涤后100℃干燥8h，得产物SCM-34，其X射线衍射图谱数据如表1所示，X射线衍射图如图1，SEM如图2。
表1
2θ(°) 相对强度，[(I/I 0)×100]
7.39 100
10.24 16
10.71 35
12.01 6
14.20 5
16.44 32
17.93 35
19.71 9
21.01 18
23.31 19
24.25 15
26.03 15
27.81 11
28.13 13
30.02 10
31.33 5
34.73 7
38.28 6
。
【实施例2】
将20.4g的异丙醇铝(Al(iPr) 3)溶于207.2mL水中，混合形成溶液C，之后将8.6g的磷酸(纯度≥85wt.％)、294.8g的四丁基氢氧化铵(40wt.％水溶液，MkSeal)以及569.1g的1-(3-氨基丙基)咪唑加入溶液C中，搅拌5h、沉化1h后得溶液C’，之后向C’溶液缓慢投入15.0g的酸性硅溶胶(Ludox HS型，40wt.％水溶液)、313.2mL的N，N-二甲基丁酰胺以及9.8mL的环己酮，搅拌2.5h后置于100℃下热处理6h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、总模板剂和总溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶模板剂R∶溶剂S＝1∶0.5∶0.75∶25∶120，模板剂R1(四丁基氢氧化铵)/模板剂R2(1-(3-氨基丙基)咪唑)＝0.1，溶剂S1(N，N-二甲基丁酰胺)/溶剂S2(环己酮)/溶剂S3(水)＝1∶0.05∶11；将上述待晶化混合物置于140℃晶化4天，产物经过滤、洗涤后120℃干燥4h，得产物SCM-34，其X射线衍射线图谱数据如表2所示，XRD图谱与图1类似。
表2
2θ(°) 相对强度，[(I/I 0)×100]
7.65 100
10.37 17
10.89 24
12.15 43
14.29 9
16.61 24
18.01 11
19.84 16
21.11 19
23.39 21
24.30 18
26.10 7
27.86 10
28.16 9
30.05 12
31.33 17
34.75 5
38.29 11
。
【实施例3】
取1021.2g的异丙醇铝溶于1078.1mL水中，混合形成溶液C，之后将432.4g的磷酸(纯度≥85wt.％)、24016.3g的四乙基氢氧化铵(40wt.％水溶液，Sigma-Aldlrich)以及54426.1g的1-(3-氨基丙基)咪唑加入溶液C中，搅拌3h、沉化6h后得溶液C’，之后向C’溶液缓慢投入450.0g的白炭黑(阿拉丁，S104573，≥99％)、4528.8mL的N，N-二甲基丁酰胺以及706.6mL的环己酮，搅拌1.5h后置于90℃下热处理11h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、总模板剂和总溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶模板剂R∶溶剂S＝1∶0.75∶0.75∶50∶90，模板剂R1(四乙基氢氧化铵)/模板剂R2(1-(3-氨基丙基)咪唑)＝0.15，溶剂S1(N，N-二甲基丁酰胺)/溶剂S2(环己酮)/溶剂S3(水)＝1∶0.25∶30；将上述待晶化混合物置于140℃晶化5天，产物经过滤、洗涤后90℃干燥10h，得产物SCM-34，其X射线衍射线图谱数据如表3所示，XRD图谱与图1类似。
表3
2θ(°) 相对强度，[(I/I 0)×100]
7.55 100
10.30 16
10.79 8
12.05 19
14.21 34
16.48 15
17.95 21
19.74 42
21.00 18
23.29 5
24.24 8
26.02 9
27.79 6
28.14 17
30.01 11
31.32 6
34.74 9
38.28 6
。
【实施例4】
取375.1g的硝酸铝溶于405.1mL水中，混合形成溶液C，之后将138.4g的磷酸(纯度≥85wt.％)、2827.6g的四丁基氢氧化铵(40wt.％水溶液，MkSeal)以及3209.7g的1-(3-氨基丙基)咪唑加入溶液C中，搅拌2h、沉化8h后得溶液C’，之后向C’溶液缓慢投入36.1g的白炭黑(阿拉丁，S104573，≥99％)、299.1mL的N，N-二甲基甲酰胺以及18.7mL的环己酮，搅拌4h后置于110℃下热处理3h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、总模板剂和总溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶模板剂R∶溶剂S＝1∶0.3∶1.2∶15∶60，模板剂R1(四丁基氢氧化铵)/模板剂R2(1-(3-氨基丙基)咪唑)＝0.17，溶剂S1(N，N-二甲基丁酰胺)/溶剂S2(环己酮)/溶剂S3(水)＝1∶0.1∶62；将上述待晶化混合物置于140℃晶化5天，产物经过滤、洗涤后120℃干燥4h，得产物SCM-34，其X射线衍射线图谱数据如表4所示，XRD图谱与图1类似。
表4
2θ(°) 相对强度，[(I/I 0)×100]
7.75 100
10.41 11
10.90 8
12.15 17
14.39 32
16.60 22
18.05 13
19.84 17
21.09 10
23.38 23
24.31 21
26.08 14
27.85 11
28.16 19
30.03 22
31.33 9
34.74 8
38.29 11
。
【实施例5】
取33.3g的硫酸铝[Al 2(SO 4) 3·18H 2O]溶于66.3mL水中，混合形成溶液C，之后将5.2g的磷酸(纯度≥85wt.％)、117.0g的四丁基氢氧化铵(40wt.％水溶液，MkSeal)以及102.6g的1-(3-氨基丙基)咪唑加入溶液C中，搅拌3h、沉化6h后得溶液C’，之后向C’溶液缓慢投入6.1g的酸性硅溶胶(Ludox HS型，40wt.％水溶液)、25.5mL的N，N-二甲基丁酰胺以及4.8mL的环己酮，搅拌4.5h后置于80℃下热处理12h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、模板剂和溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶总模板剂R∶总溶剂S＝1∶0.4∶0.9∶10∶80，模板剂R1(四丁基氢氧化 铵)/模板剂R2(1-(3-氨基丙基)咪唑)＝0.22，溶剂S1(N，N-二甲基丁酰胺)/溶剂S2(环己酮)/溶剂S3(水)＝1∶0.3∶48；将上述待晶化混合物置于140℃晶化5天，产物经过滤、洗涤后100℃干燥8h，得产物SCM-34，其X射线衍射线图谱数据如表5所示，XRD图谱与图1类似。
表5
2θ(°) 相对强度，[(I/I 0)×100]
7.50 100
10.27 16
10.76 9
12.03 21
14.20 11
16.45 35
17.87 25
19.71 31
20.95 17
23.31 16
24.23 25
26.01 5
27.79 17
28.14 24
30.02 23
31.33 9
34.73 9
38.28 6
。
【实施例6】
取266.6g的硫酸铝溶于157.5mL水中，混合形成溶液C，之后将50.7g的磷酸(纯度≥85wt.％)、614.6g的四乙基氢氧化铵(25wt.％水溶液)以及801.3g的N-乙基-2-氨甲基吡咯烷(纯度95％，迈瑞尔)加入溶液C中，搅拌4.5h、沉化3.5h后得溶液C’，之后向C’溶液缓慢 投入18.1g的酸性硅溶胶(Ludox HS型，40wt.％水溶液)、124.9mL的N，N-二甲基甲酰胺以及60.2mL的1，4-二氧六环，搅拌3.5h后置于80℃下热处理12h形成均匀的待晶化混合物，其中以Al 2O 3计的铝源、以SiO 2计的硅源、以P 2O 5计的磷源、模板剂和溶剂的摩尔比为：Al 2O 3∶SiO 2∶P 2O 5∶总模板剂R∶总溶剂S＝1∶0.3∶1.1∶20∶100，模板剂R1(四乙基氢氧化铵)/模板剂R2(N-乙基-2-氨甲基吡咯烷)＝0.15，溶剂S1(N，N-二甲基丁酰胺)/溶剂S2(1，4-二氧六环)/溶剂S3(水)＝1∶0.4∶22；将上述待晶化混合物置于140℃晶化5天，产物经过滤、洗涤后100℃干燥8h，得产物SCM-34，其X射线衍射线图谱数据如表6所示，XRD图谱与图1类似。
表6
2θ(°) 相对强度，[(I/I 0)×100]
7.50 100
10.27 16
10.76 17
12.03 27
14.20 13
16.45 23
17.87 14
19.71 41
20.95 15
23.31 10
24.23 33
26.01 6
27.79 7
28.14 14
30.02 28
31.33 7
34.73 8
38.28 9
。
二、含金属的AFI型分子筛的合成和应用
1、由SCM-34分子筛合成含金属的AFI型分子筛
【实施例7】
室温状态下，将136.2g实施例1得到的SCM-34分子筛、34.7g的三乙胺[TEA]、237.6g的四乙基溴化铵[TEABr]以及12008.3g的去离子水充分搅拌后，置于80℃热处理0.5h得到前驱体A。称取1.4g的硝酸镁[Mg(NO 3) 2·6H 2O，纯度≥98wt.％]溶于1161.7mL去离子水中，充分搅拌1.5h后形成混合物B。将前驱体A密闭搅拌状态下投入混合物B中，继续搅拌3.5h后，置于85℃下继续搅拌1h；再置于160℃晶化10min，经过滤、洗涤后100℃干燥6h，然后升温至600℃，恒温焙烧4h，即得AFI分子筛(下同)，记为SSP5-1，经ICP测试，SSP5-1中含有0.18wt.％的Mg元素，其XRD图类似于图3，SEM图类似于图4和图5，产物中金属含量、酸分布情况列于表7。
【实施例8】
室温状态下，将20.8g的实施例2得到的SCM-34分子筛、208g的三乙胺[TEA]、4.2g的白炭黑[SiO 2，99wt.％]以及685.6g的去离子水，充分搅拌后，置于60℃热处理1h得到前驱体A。称取1.1g的硝酸钴[Co(NO 3) 2·4H 2O，纯度≥99wt.％]、6.3g的白炭黑[SiO 2，99wt.％]溶于354.4mL去离子水中，充分搅拌2.5h后形成混合物B。将前驱体A密闭搅拌状态下投入混合物B中，继续搅拌0.5h后，置于100℃密闭搅拌0.5h；将上述搅拌混合物，再置于110℃晶化120min，经过滤、洗涤后90℃干燥8h，然后升温至500℃，恒温焙烧8h，即得产物，记为SSP5-2，经ICP测试，SSP5-2中含有0.01wt.％的Co元素，其XRD图类似于图3，SEM图类似于图4和图5，产物中金属含量、酸分布情况列于表7。
【实施例9】
室温状态下，将12110.7g实施例4得到的SCM-34分子筛、8106.3g的苄基三乙基氯化铵[TEBAC，99wt.％]、4004.4g的四乙基氢氧化铵[TEAOH，50％]以及15363.4g的酸性硅溶胶[SiO 2，40wt.％]充分搅拌形1.5h后置于60℃热处理1.5h得到前驱体A。称取6055.4g的硝酸锌[Zn(NO 3) 2·6H 2O，纯度≥99wt.％]、15363.4g的酸性硅溶胶[SiO 2，40wt.％]溶于4052.9mL去离子水中，充分搅拌2.5h后形成混合物B。将前驱体 A密闭搅拌状态下投入混合物B中，继续搅拌0.5h后，置于90℃密闭搅拌0.9h；将上述搅拌混合物，再置于115℃晶化86min，经过滤、洗涤后80℃干燥9h，然后升温至550℃，恒温焙烧5h即得产物，记为SSP5-3，经ICP测试，SSP5-3中含有1.0wt.％的Zn元素，其XRD图为图3，SEM图为图4和图5，TPD图为图6，产物中金属含量、酸分布情况列于表7。
表7
Figure PCTCN2021117344-appb-000002
2、含金属的AFI分子筛在甲醇转化制烃反应中的应用
【实施例10】
取实施例7合成的SSP5-1分子筛，在550℃下焙烧4h，冷却至室温后压片、敲碎、筛分，取12～20目的颗粒备用。以甲醇为原料，用直径为15毫米的固定床反应器，在505℃、质量空速3.5h -1、压力为1.7MPa的条件下考评，乙烯、丙烯、丁烯收率达到96.8％，取得了较好的技术效果。
【实施例11】
取实施例8合成的SSP5-2分子筛，在550℃下焙烧4h，冷却至室温后压片、敲碎、筛分，取12～20目的颗粒备用。以甲醇为原料，用直径为15毫米的固定床反应器，在400℃、质量空速0.5h -1、压力为5.1MPa的条件下考评，乙烯、丙烯、丁烯收率达到92.6％，取得了较好的技术效果。
【实施例12】
取实施例9合成的SSP5-3分子筛，在550℃下焙烧4h，冷却至室温后压片、敲碎、筛分，取12～20目的颗粒备用。以甲醇为原料，用直径为15毫米的固定床反应器，在600℃、质量空速0.1h -1、压力为0.01MPa的条件下考评，乙烯、丙烯、丁烯收率达到90.9％，取得了较好的技术效果。
三、SAPO-17分子筛的合成和应用
1、由SCM-34分子筛合成SAPO-17分子筛
【实施例13】
室温状态下，将2.6g的哌嗪(PIP)、8.5g的1、4-二氧六环(DOA)充分搅拌，然后置于90℃热处理1.0h后得到前驱体P 1。称取5.6g实施例3制备的SCM-34分子筛以及3.1g的白炭黑(SiO 2)混合于6.9g的1、4-二氧六环溶液中，并于40℃热处理5h得到混合物料M 1。将前驱体P 1剧烈搅拌状态下投入混合物料M 1，继续搅拌2.5h后，形成待晶化混合物；置于110℃下继续搅拌0.5h，再置于140℃晶化1h，产物经过滤、洗涤后120℃干燥4h，然后升温至500℃，恒温焙烧6h即得SAPO-17分子筛，记为STE-1，其XRD图谱见图7，其SEM图见图8。
【实施例14】
室温状态下，将666.7g的1，10-邻菲罗啉(1，10-PIH)、731.3g的哌嗪(PIP)以及1285.2g的1，2-环氧环戊烷(CPO)充分搅拌，然后置于40℃热处理5h得到前驱体P 2。称取239.8g实施例5制备的SCM-34分子筛混合于139.8g的1，2-环氧环戊烷(CPO)溶液中，并于90℃热处理1.0h得到混合物料M 2。将前驱体P 2剧烈搅拌状态下投入混合物料M 2，继续搅拌4.0h后，置于80℃密闭搅拌5h；再置于130℃晶化2h，产物经过滤、洗涤后100℃干燥6h，然后升温至600℃，恒温焙烧4h即得产物，记为STE-2。其XRD图谱与图7类似，其SEM图与图8类似。
【实施例15】
室温状态下，将0.8g的环己胺(HCHA)、33.7g的哌嗪(PIP)、5.5g的1、4-二氧六环(DOA)以及5.2g的环己酮(CHO)充分搅拌，然后置于55℃热处理4.0h得到前驱体P 3。称取6.9g实施例6制备的SCM-34分子筛混合于5.0g的1、4-二氧六环(DOA)以及5.7g的环己酮(CHO)溶液中，并于70℃热处理2.0h得到混合物料M 3。将前驱体P 3剧烈搅拌状态下投入混合物料M 3，继续搅拌1h后，置于100℃密闭搅拌1h；再置于120℃晶化5h，产物经过滤、洗涤后80℃干燥9h，然后升温至400℃，恒温焙烧8h即得产物，记为STE-3。其XRD图谱与图7类似，其SEM图与图8类似。
【对比例1】
依据CN103922361A中所公开SAPO-17分子筛的合成方法制备SAPO-17分子筛，具体如下：以异丙醇铝为铝源，磷酸为磷源，硅溶胶为硅源，环己胺为模板剂，将81g的异丙醇铝加入到48.9g的超纯水中，搅拌均匀后加入45.7g磷酸(85wt.％)，搅拌1h之后，向混合液中加入11.5mL的环己胺，搅拌老化2h后，向体系中添加30wt.％的SiO 2的水溶液11.9g，继续老化数小时后将溶胶置于含聚四氟乙烯内衬的不锈钢反应釜中在200℃晶化120h，得形貌为短粗的棒状SAPO-17分子筛，其XRD图谱见图9，其SEM图见图10
【对比例2】
依据文献(天津化工，2016，30(3)：17-19.)所述的SAPO-17分子筛的合成方法，具体为：以异丙醇铝为铝源，磷酸为磷源，硅溶胶为硅源，环己胺为模板剂，依具反应配比为1Al 2O 3∶1P 2O 5∶0.3SiO 2∶1CHA∶1HF∶40H 2O，固定铝源用量为0.015mol的方案，将3.06g的异丙醇铝加入到5.4g的去离子水中，搅拌均匀后加入1.7g的磷酸(85wt.％)，继续搅拌1.5h后，向混合溶液中加入0.7g的环己胺，搅拌老化1.5h后，继续向反应体系中添加2.25g的硅溶胶(40wt.％)，继续搅拌至数小时后，将溶胶置于含聚四氟乙烯内衬的不锈钢反应釜中在于200℃晶化120h得到SAPO-17分子筛。
2、SAPO-17分子筛的应用
(1)SAPO-17分子筛在甲醇制烃反应中的应用
【实施例16】
取实施例13合成的STE-1分子筛，在550℃下焙烧4h，冷却至室温后压片、敲碎、筛分，取12～20目的颗粒备用。以甲醇为原料，用直径为15毫米的固定床反应器，在600℃、质量空速4.9h -1、压力为1.0MPa的条件下考评，甲醇转化率100％，产物中乙烯、丙烯收率达到78.7％，选择性比率(乙烯/丙烯)＝2.87，取得了较好的技术效果。
【实施例17】
取实施例14合成的STE-2分子筛，采用实施例16的催化剂制备方法制得催化剂，以甲醇为原料，用直径为15毫米的固定床反应器，在550℃、质量空速15h -1、压力为10MPa的条件下考评，甲醇转化率100％，产物中乙烯、丙烯收率达到80.8％，选择性比率(乙烯/丙烯)＝2.76，取得了较好的技术效果。
【实施例18】
取实施例15合成的STE-3分子筛，采用实施例16的催化剂制备方法制得催化剂，以甲醇为原料，用直径为15毫米的固定床反应器，在474℃、质量空速7.1h -1、压力为2.4MPa的条件下考评，甲醇转化率100％，产物中乙烯、丙烯收率达到84.5％，选择性比率(乙烯/丙烯)＝2.99，取得了较好的技术效果。
【对比例3】
选取对比例1合成的SAPO-17分子筛，采用实施例16的催化剂制备方法制得催化剂，按照实施例17的方式考评，甲醇转化率100％，产物中乙烯、丙烯收率达到33.3％，选择性比率(乙烯/丙烯)＝1.1。
【对比例4】
选取对比例2合成的SAPO-17分子筛，采用实施例16的催化剂制备方法制得催化剂，按照实施例18的方式考评，甲醇转化率100％，产物中乙烯、丙烯收率达到40.1％，选择性比率(乙烯/丙烯)＝1.2。
(2)SAPO-17分子筛在合成气制烃类反应中的应用
【实施例19】
SAPO-17分子筛在合成气制烃类反应中的应用
取实施例13合成的STE-1分子筛，在550℃下焙烧6h，然后压片、敲碎、筛分，取20～40目的颗粒，并使用催化剂填料质量比为ZnCrO x/STE＝1.0(ZnCrO x代表氧化锌和氧化铬的混合物，制得氧化物-分子筛催化剂备用)。以合成气为原料，用直径为15毫米的固定床反应器，工艺条件为：反应温度400℃，压力10MPa，空速2000h -1，合成气构成H 2/CO＝0.5∶1，CO的转化率为41.9％，其中C 2-C 4烯烃选择性为66.9％，选择性比率(乙烯/丙烯)＝2.61。
【实施例20】
SAPO-17分子筛在合成气制烃类反应中的应用
取实施例14合成的STE-2分子筛，采用实施例19的催化剂制备方法制得催化剂。工艺条件为：反应温度375℃，压力7.5MPa，空速1000h -1，合成气构成H 2/CO＝0.66∶1，CO的转化率为45.6％，其中C 2-C 4烯烃选择性为75.6％，选择性比率(乙烯/丙烯)＝2.66。
【实施例21】
SAPO-17分子筛在合成气制烃类反应中的应用
取实施例15合成的STE-3分子筛，采用实施例19的催化剂制备方法制得催化剂。工艺条件为：反应温度350℃，压力1.2MPa，空速500h -1，合成气构成H 2/CO＝0.75∶1，CO的转化率为51.7％，其中C 2-C 4烯烃选择性为85.6％，选择性比率(乙烯/丙烯)＝2.98。
【对比例5】
SAPO-17分子筛在合成气制烃类反应中的应用
选取对比例2合成的SAPO-17分子筛，采用实施例20的催化剂制备方法制得催化剂，按照实施例20的方式考评，CO的转化率为22.3％，其中C 2-C 4烯烃选择性为36.8％，选择性比率(乙烯/丙烯)＝1.21。
由以上对比试验可以看出，本发明所制备的SAPO-17分子筛在甲醇转化制烃的反应中乙烯、丙烯收率更高，选择性比率(乙烯/丙烯)也更高；本发明所制备的SAPO-17分子筛在合成气制烃类反应中C 2 ＝～C 4 ＝选择性更高，选择性比率(乙烯/丙烯)也更高。

Claims (15)

  1. 一种SCM-34分子筛，其特征在于，所述SCM-34分子筛包含铝，磷，氧和任选的硅；所述分子筛的XRD衍射数据中，2θ角在5-50°范围内最强峰的2θ角为7.59±0.2；所述SCM-34分子筛的X射线衍射图谱包括如下表所示的X射线衍射峰：
    2θ(°) 相对强度，[(I/I 0)×100] 7.59±0.2 100 10.81±0.1 5-50 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50
    。
  2. 按照权利要求1所述的SCM-34分子筛，其特征在于，所述SCM-34分子筛具有如式“Al 2O 3：xSiO 2：yP 2O”所示的示意性化学组成，其中，0≤x≤0.5，0.75≤y≤1.5；所述分子筛的XRD衍射数据中，2θ角在5-50°范围内最强峰的2θ角为7.59±0.2；所述SCM-34分子筛的X射线衍射图谱包括如下表所示的X射线衍射峰：
    2θ(°) 相对强度，[(I/I 0)×100] 7.59±0.2 100 10.81±0.1 5-50 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50 34.74±0.05 5-50
    。
  3. 按照权利要求1或2所述的分子筛，其特征在于，所述SCM-34分子筛的X射线衍射图谱还包括如下表所示的X射线衍射峰：
    2θ(°) 相对强度，[(I/I 0)×100] 14.25±0.1 5-50 21.01±0.1 10-20
    24.27±0.05 5-50 26.05±0.05 5-50 27.82±0.05 5-50 28.15±0.02 5-50 30.03±0.02 5-50
    。
  4. 按照权利要求1-3任一项所述的分子筛，其特征在于，所述SCM-34分子筛的X射线衍射图谱还包括如下表所示的X射线衍射峰：
    2θ(°) 相对强度，[(I/I 0)×100] 10.33±0.1 10-20 12.09±0.1 5-50 19.77±0.1 5-50 31.33±0.01 5-50 38.29±0.01 5-50
    。
  5. 一种按照权利要求1-4任一项所述SCM-34分子筛的制备方法，包括：将含有铝源、磷源、有机模板剂R1和有机模板剂R2、溶剂S1、溶剂S2和溶剂S3、和任选加入的硅源的混合物进行晶化处理，得到SCM-34分子筛；
    其中，所述有机模板剂R1选自季铵盐和/或季铵碱中的一种或几种；有机模板剂R2选自咪唑，吡咯烷，和其衍生物中的一种或几种；溶剂S1选自酰胺基溶剂中的一种或几种；溶剂S2选自环状有机溶剂中的一种或几种；溶剂S3选自水和低碳醇中的一种或几种，其中有机模板剂R1和有机模板剂R2代表彼此不同的有机模板剂，以及溶剂S1、溶剂S2和溶剂S3代表彼此不同的溶剂。
  6. 按照权利要求5所述的方法，其特征在于，所述有机模板剂R1选自四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、四丙基氢氧化铵、四丁基溴化铵、四丁基氢氧化铵中的一种或几种；所述有机模板剂R2选自咪唑、2-甲基咪唑、4-甲基咪唑、1-(3-氨基丙基)咪唑、2-乙基-4-甲基咪唑、吡咯烷、1-(3-吡咯烷)吡咯烷、N-乙基-2-氨甲基吡咯烷中的一种或几种；所述溶剂S1选自N，N-二甲基甲酰胺、N，N-二甲 基乙酰胺、N，N-二乙基甲酰胺和N，N-二丁基甲酰胺中的一种或几种；所述溶剂S2选自1，4-二氧六环、环己烷、环己酮和环己醇中的一种或几种；和/或，所述溶剂S3选自甲醇、乙醇、乙二醇、丁醇和水中的一种或多种。
  7. 按照权利要求5或6所述的方法，其特征在于，所述混合物中，铝源以Al 2O 3计、硅源以SiO 2计、磷源以P 2O 5计、有机模板剂R1+R2、溶剂S1+S2+S3的摩尔组成如下：SiO 2/Al 2O 3＝0～1，优选为0.1～0.75；P 2O 5/Al 2O 3＝0.5～2，优选为0.75～1.5；模板剂R1+R2/Al 2O 3＝1～200，优选为5～50；溶剂S1+S2+S3/Al 2O 3＝5～500，优选为35～120。
  8. 按照权利要求5-7任一项所述的方法，其特征在于，所述有机模板剂R1与有机模板剂R2的摩尔比为0.01～1∶1，优选为0.1～0.25∶1；所述溶剂S1、溶剂S2、与溶剂S3的摩尔比为1∶0.01～1∶1～100，优选为1∶0.05～0.5∶10～80。
  9. 按照权利要求5-8任一项所述的方法，其特征在于，所述晶化处理的条件包括：晶化温度为120～200℃，优选为140～180℃，更优选为140～160℃；晶化时间为1～5天，优选为3～5天，更优选为4～5天。
  10. 一种分子筛组合物，其特征在于，包括权利要求1-4任一所述的分子筛或按照权利要求5-9任一项方法制备的分子筛，以及粘结剂。
  11. 权利要求1-4任一所述的分子筛或按照权利要求5-9任一项方法制备的分子筛在制备含金属的AFI分子筛或SAPO-17分子筛中的应用。
  12. 一种制备含金属的AFI分子筛的方法，其包括：采用权利要求1-4任一所述的分子筛或按照权利要求5-9任一项方法制备的分子筛作为反应物原料，与溶剂SI、有机模板剂R、选择性加入的第一硅源混合制备前驱体A，然后与溶剂SII、金属源、选择性加入的第二硅源混合，制备得到所述AFI分子筛。
  13. 一种制备SAPO-17分子筛的方法，其包括：
    1)将有机模板剂cR及第一有机溶剂cS混合，进行第一热处理，得到前驱体P；
    2)将本发明的SCM-34分子筛、选择性加入的硅源与第二有机溶剂cS混合，进行第二热处理，得到混合物料M；
    3)将步骤1)所得前驱体P与步骤2)所得混合物料M混合，形 成待晶化混合物；
    4)将步骤3)得到的待晶化混合物进行预处理，然后进行晶化反应，得到SAPO-17分子筛。
  14. 根据权利要求12所述的方法获得的含金属的AFI分子筛在甲醇转化制烃反应中的应用。
  15. 根据权利要求13所述的方法获得的SAPO-17分子筛在甲醇制烃反应中或者在合成气制烃类反应中的应用。
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