KR-102961787-B1 - SCM-34 molecular sieve, method of manufacturing the same, and uses the same

Abstract

The present invention discloses an SCM-34 molecular sieve, a method for manufacturing the same, and uses. The SCM-34 molecular sieve comprises aluminum, phosphorus, oxygen, and optionally silicon. In the XRD diffraction data of the molecular sieve, the 2θ angle of the strongest peak within the 5-50° range is 7.59±0.2. The SCM-34 molecular sieve has a novel skeletal structure and can be used in the manufacture of metal-containing AFI type molecular sieves or SAPO-17 molecular sieves, thereby meeting various requirements for catalysts in chemical production.

Inventors

• 양, 웨이민
• 치아오, 지안
• 위안, 지칭
• 왕, 젠동
• 텡, 지아웨이
• 타오, 웨이촨
• 푸, 웬후아
• 리우, 송린

Assignees

• 차이나 페트로리움 앤드 케미컬 코포레이션
• 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙

Dates

Publication Date

20260507

Application Date

20210909

Priority Date

20200914

Claims (15)

1. An SCM-34 molecular sieve comprising aluminum, phosphorus, oxygen, and optionally silicon; wherein, in the XRD diffraction data of the molecular sieve, the 2θ angle of the strongest peak within the range of 5-50° is 7.59 ± 0.2; and wherein the X-ray diffraction pattern of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the table below.
2. The SCM-34 molecular sieve according to claim 1, wherein the SCM-34 molecular sieve has a schematic chemical composition as represented by the chemical formula " Al₂O₃ : xSiO₂ : yP₂O " (where 0≤x≤0.5, 0.75≤y≤1.5 ); wherein, in the XRD diffraction data of the molecular sieve, the 2θ angle of the strongest peak within the range of 5-50° is 7.59 ± 0.2; and wherein the X-ray diffraction pattern of the SCM-34 molecular sieve includes the X-ray diffraction peaks shown in the table below.
3. An SCM-34 molecular sieve according to claim 1 or 2, characterized in that the X-ray diffraction pattern of the SCM-34 molecular sieve further includes the X-ray diffraction peaks shown in the table below.
4. An SCM-34 molecular sieve according to claim 1 or 2, characterized in that the X-ray diffraction pattern of the SCM-34 molecular sieve further includes the X-ray diffraction peaks shown in the table below.
5. A method for manufacturing an SCM-34 molecular sieve according to claim 1 or 2, The method comprises the step of obtaining an SCM-34 molecular sieve by crystallizing a mixture comprising an aluminum source, a phosphorus source, organic templates R1 and R2, solvents S1, S2 and S3, and optionally a silicon source; A method for manufacturing, wherein the organic template R1 is selected from one or more of quaternary ammonium salts and/or quaternary ammonium bases; the organic template R2 is selected from one or more of imidazole, pyrrolidine, and derivatives thereof; the solvent S1 is selected from one or more of amide group solvents; the solvent S2 is selected from one or more of cyclic organic solvents; and the solvent S3 is selected from one or more of water and lower alcohols, wherein the organic template R1 and the organic template R2 represent different organic templates, and the solvent S1, the solvent S2, and the solvent S3 represent different solvents.
6. In claim 5, the organic template R1 is selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide; the organic template R2 is selected from one or more of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1-(3-pyrrolidine)pyrrolidine, and N-ethyl-2-aminomethylpyrrolidine; and the solvent S1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N,N-dibutylformamide; A method for manufacturing, characterized in that the solvent S2 is selected from one or more of 1,4-dioxane, cyclohexane, cyclohexanone, and cyclohexanol, and/or; and the solvent S3 is selected from one or more of methanol, ethanol, ethylene glycol, butanol, and water.
7. A method for manufacturing according to claim 5, wherein, in the mixture, the molar composition of the aluminum source based on Al₂O₃, the silicon source based on SiO₂, the phosphorus source based on P₂O₅ , the organic template R1+R2, and the solvent S1+S2+S3 is: SiO₂ / Al₂O₃ = 0 ~ 1 , or 0.1~ 0.75 ; P₂O₅ / Al₂O₃ = 0.5~2, or 0.75~1.5; template R1+R2/ Al₂O₃ = 1~200, or 5~50; solvent S1+S2+ S3 / Al₂O₃ = 5~500, or 35~120 .
8. A method for manufacturing according to claim 5, characterized in that the molar ratio of the organic template R1 to the organic template R2 is 0.01 to 1:1 or 0.1 to 0.25:1; and the molar ratio of the solvent S1, the solvent S2, and the solvent S3 is 1:0.01 to 1:1 to 100 or 1:0.05 to 0.5:10 to 80.
9. A manufacturing method according to claim 5, wherein the conditions for the crystallization treatment include a crystallization temperature of 120 to 200°C, or 140 to 180°C, or 140 to 160°C; and a crystallization time of 1 to 5 days, or 3 to 5 days, or 4 to 5 days.
10. A molecular sieve composition characterized by comprising an SCM-34 molecular sieve according to claim 1 or 2 and a binder.
11. A method of using an SCM-34 molecular sieve according to claim 1 or 2 in the manufacture of a metal-containing AFI type molecular sieve or a SAPO-17 molecular sieve.
12. A method for manufacturing a metal-containing AFI type molecular sieve, comprising using an SCM-34 molecular sieve according to claim 1 or 2 as a reaction raw material, mixing it with a solvent SI, an organic template R, and an optionally added first silicon source to produce a precursor A, and then mixing the precursor A with a solvent SII, a metal source, and an optionally added second silicon source to produce the AFI molecular sieve.
13. As a method for preparing a SAPO-17 molecular sieve: 1) A step of mixing an organic template cR and a first organic solvent cS and performing a first heat treatment to obtain a precursor P; 2) A step of mixing an SCM-34 molecular sieve according to claim 1 or 2, an optionally added silicon source, and a second organic solvent cS, and performing a second heat treatment to obtain a mixed material M; 3) A step of mixing the precursor P obtained in Step 1) with the mixed material M obtained in Step 2) to form a mixture to be crystallized; 4) Pre-treating the mixture to be crystallized obtained in Step 3), and then performing a crystallization reaction to obtain the SAPO-17 molecular sieve. A manufacturing method comprising
14. A method of using a metal-containing AFI type molecular sieve obtained by the manufacturing method according to claim 12 in a reaction for converting methanol into hydrocarbons.
15. A method of using a SAPO-17 molecular sieve obtained by the manufacturing method according to claim 13 in a reaction of methanol to hydrocarbon or a reaction of syngas to hydrocarbon.

Description

SCM-34 molecular sieve, method of manufacturing the same, and uses the same The present invention relates to the field of molecular sieves, in particular to SCM-34 molecular sieves, methods for manufacturing the same, and uses the same. Porous materials are a type of solid compound having a regular pore structure. According to the definition by the International Union of Pure and Applied Chemistry (IUPAC), porous materials with a pore diameter of less than 2 nm are classified as micropore materials; porous materials with a pore diameter exceeding 2 nm are classified as mesopore materials or macropore materials (pore diameter exceeding 50 nm). Molecular sieve materials are a type of porous material that generally has a pore channel diameter of less than 2 nm, belongs to the micropore material category, and is primarily characterized by selective adsorption. Their unique pore channel system, from which the name "molecular sieve" is derived, enables them to sieve small molecules of various sizes. In addition, these materials have a wide range of internal pore cavity sizes and possess rich and diverse topological structures, and have been widely used in fields such as adsorption separation, heterogeneous catalysis, carriers of various guest molecules, and ion exchange, and excellent technical results have been achieved. Traditional zeolite molecular sieves are a type of crystalline silicate material, generally formed by connecting silicon-oxygen tetrahedra [ SiO₄ ] ₄- and aluminum-oxygen tetrahedra [ AlO₄ ] ₅- through shared oxygen atoms, commonly referred to as the TO₄ tetrahedron (the main structural unit), where the silicon element can also be partially isomorphically substituted by other elements, particularly some trivalent or tetravalent elements such as Al, B, Ga, Ge, and Ti. Due to certain specific characteristics of their structure and chemical properties, zeolite molecular sieves are widely used in catalysis, adsorption, ion exchange, and other fields. The key factor determining the application performance of molecular sieves is the characteristics of their pore channels or cages, which are determined by the sieve's inherent crystal structure. Therefore, obtaining molecular sieves with novel crystal structures is of great significance for developing molecular sieve applications. In 1982, scientists St. Wilson and E.M. Flanigen et al. at the United States Union Carbide Corp. (UCC) successfully synthesized and developed a completely new family of molecular sieves: the aluminophosphate molecular sieve AlPO₄ -n (n represents the model number, US 4310440), using aluminum sources, phosphorus sources, and organic templates. Two years later, based on AlPO₄ -n, UCC successfully produced another series of silicoaluminophosphate molecular sieves, SAPO-n (n represents the model number), by partially replacing the Al and P atoms of the AlPO₄ framework with Si atoms. After replacing the P or Al atoms of the original AlPO₄ framework with Si atoms, a non-neutral skeleton composed of SiO₄ , AlO₄ , and PO₄ tetrahedra is formed in the SAPO-n structure. In this type of molecular sieve framework, silicon exists in two ways: (1) replacing one P atom with one Si atom; and (2) replacing a pair of aluminum and phosphorus atoms with two silicon atoms, respectively. A representative SAPO-n molecular sieve is the SAPO-34 molecular sieve, which has a topological structure of CHA. The molecular sieve has a framework structure similar to chabasite and belongs to the cubic system. The structural motif consists of AlO₂- , SiO₂ , and PO₂ + tetrahedra. The framework includes an ellipsoidal supercage and a three-dimensional cross structure containing 8-membered ring pore channels. The pore diameter of the 8-membered ring pore channels is approximately 0.38 nm. The supercage has a pore opening diameter maintained at 0.43 to 0.50 nm. Due to its appropriate proton acidity, larger specific surface area, superior adsorption performance, superior thermal stability, superior hydrothermal stability, and superior shape selectivity of the pore channel structure for light olefins, SAPO-34 molecular sieve has been successfully commercialized as a methanol to light olefins (MTO) catalyst and exhibits very excellent catalytic activity and selectivity. Currently, most molecular sieves with known topological structures are produced by hydrothermal or solvothermal synthesis. The key steps of a typical hydrothermal or solvothermal synthesis method are as follows: First, reactants such as a metal source, a non-metal source, an organic template, and a solvent are uniformly mixed to obtain an initial sol, i.e., the mixture to be crystallized; then, the mixture is placed in a reactor lined with PTFE and with a stainless steel outer wall, sealed, and subjected to a crystallization reaction under a constant temperature and autogenous pressure—similar to the process of rock formation on Earth—i.e., the precipitation of molecular sieve crystals from the crystall