WO2008019584A1 - Procédé de synthèse d'un tamis moléculaire sapo-34 enrichi avec une structure si(4ai) dans le squelette - Google Patents

Procédé de synthèse d'un tamis moléculaire sapo-34 enrichi avec une structure si(4ai) dans le squelette Download PDF

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Publication number
WO2008019584A1
WO2008019584A1 PCT/CN2007/002333 CN2007002333W WO2008019584A1 WO 2008019584 A1 WO2008019584 A1 WO 2008019584A1 CN 2007002333 W CN2007002333 W CN 2007002333W WO 2008019584 A1 WO2008019584 A1 WO 2008019584A1
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WO
WIPO (PCT)
Prior art keywords
molecular sieve
sapo
gel mixture
mixture
skeleton
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PCT/CN2007/002333
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English (en)
Chinese (zh)
Inventor
Lei Xu
Zhongmin Liu
Peng Tian
Aiping Du
Lixin Yang
Cuiyu Yuan
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Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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Application filed by Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences filed Critical Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Publication of WO2008019584A1 publication Critical patent/WO2008019584A1/fr

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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)
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • 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
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a method for synthesizing SAPO-34 molecular sieve with a skeleton rich in Si(4Al) structure.
  • the molecular sieve is calcined and used in methanol to produce an olefin catalyst, which can effectively improve the selectivity of ethylene and propylene. Background technique
  • SAPO molecular sieves are a class of crystalline silicoaluminophosphates, consisting of P0 4 +, A10 4 —, and The tetrahedron of Si0 4 constitutes a three-dimensional skeleton structure.
  • MTO methanol to olefin
  • SAPO-34 molecular sieve exhibits excellent catalytic performance in MTO reaction due to its suitable acidity and pore structure.
  • the acidity of the SAPO type molecular sieve can be regarded as caused by the substitution of Si into the framework of the aluminum phosphate molecular sieve by substitution.
  • the aluminum phosphate molecular sieve ⁇ 1 ⁇ 0 4 - ⁇ is composed of ⁇ 10 2 ⁇ tetrahedron and ⁇ 0 2 + tetrahedron in strict proportion of 1:1, the whole skeleton is electrically neutral, there is no obvious Briinsted acid (tannic acid) center, and the whole The acidity is very weak.
  • Si atoms can be connected with 0 to 4 aluminum atoms through oxygen to form various Si coordination structures, which can be represented separately. It is Si(0Al), Si(lAl), Si(2Al), Si(3Al), Si(4Al).
  • the acid center strength of different silicon-aluminum structures is enhanced in the order of Si(OAl), Si(4Al), Si(3Al), Si(2Al), Si(lAl), so the strength of the acid center in the molecular sieve framework
  • the number and number are closely related to the structure and number of the skeleton silicon atoms (J. Phys.
  • An object of the present invention is to provide a method for synthesizing SAPO-34 molecular sieve having a skeleton rich in Si(4Al) structure.
  • Another object of the present invention is to provide a SAPO-34 molecular sieve having a skeleton rich in Si(4Al) structure.
  • the present invention has been completed through intensive work by the inventors.
  • a method of synthesizing a SAPO-34 molecular sieve having a framework rich in Si(4Al) structure comprising the steps of:
  • the templating agent is one of triethylamine and diethylamine, or a mixture of the two.
  • the SiO 2 in the step a) is derived from a mixture of one or both of a silica sol and white carbon black.
  • A1 2 0 3 is derived from a mixture of one or both of activated alumina and pseudoboehmite.
  • P 2 0 5 in the step a) is derived from phosphoric acid.
  • the crystallization time in the step c) is from 2 to 120 hours.
  • a SAPO-34 molecular sieve obtained according to the method described above.
  • the Si/Al molar ratio in the SAPO-34 molecular sieve framework is
  • Fig. 1 is an XRD chart of a product synthesized under different silicon content conditions in Example 1 of the present invention.
  • Figure 2 29 Si NMR spectrum of samples Nos. SP34-1, SP34-2, SP34-3 and SP34-4 in Example 2, Comparative Example 2. detailed description
  • Another object of the present invention is to synthesize a SAPO-34 molecular sieve having a skeleton rich in Si(4Al) structure.
  • the synthesized molecular sieve with Si(4Al) as the main coordination environment can be used to improve the selectivity of ethylene and propylene by calcination and methanol for the catalyst.
  • the technical solution of the present invention is to provide a method for synthesizing a SAPO-34 molecular sieve having a skeleton rich in Si(4Al) structure, which synthesizes the proportion of silicon added to the initial gel by modulation, thereby controlling the shape
  • the morphology and quantity of the Si coordination environment of the molecular sieve framework were synthesized, and the SAPO-34 molecular sieve with the Si (4Al) structure of the skeleton Si coordination environment was synthesized;
  • the molar ratio of each component of the initial gel mixture is:
  • Si0 2 /Al 2 0 3 0.1 -2.0;
  • R is a templating agent.
  • the templating agent is one or a mixture of two of triethylamine and diethylamine.
  • the low Si content of the SAPO-34 molecular sieve is adjusted by adjusting the initial gel silica-alumina ratio, and the skeleton Si/Al molar ratio is 0.05 to 0.15.
  • the synthesized low silicon content SAPO-34 molecular sieve skeleton Si coordination environment is a Si (4Al) structure.
  • the synthesized SAPO-34 molecular sieve catalyst with Si(4Al) as a coordination environment is applied to the methanol to olefin reaction, which can effectively improve the selectivity of ethylene and propylene.
  • the invention is characterized in that a low silicon content SAPO-34 molecular sieve having only a Si(4Al) coordination environment can be synthesized by adjusting the proportion of silicon in the initial gel.
  • the invention synthesizes and synthesizes the Si coordination environment on the surface of SAPO-34 molecular sieve, can adjust the kind and number of coordination environment of molecular sieve skeleton Si, and selects and controls the synthesis of SAPO-34 molecular sieve catalyst with Si(4Al) as the main coordination environment.
  • the reaction of methanol to olefin can increase the selectivity of ethylene and propylene, and can greatly improve the life of the catalyst.
  • step b) adding a metered templating agent to the first gel mixture obtained in step a) to obtain a second gel mixture; c) loading the second gel mixture obtained in step b) into a lining of polytetrafluoroethylene In a stainless steel synthesis kettle, it is hermetically heated to a crystallization temperature, and is subjected to constant temperature crystallization under autogenous pressure.
  • 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; d) the original SAPO-34 molecular sieve obtained in the step c) The powder was calcined in 400-60 CTC air for 3-8 hours to obtain a SAPO-34 molecular sieve catalyst.
  • R is a templating agent.
  • SiO 2 is derived from a mixture of one or both of silica sol and white carbon;
  • A1 2 0 3 is derived from a mixture of one or both of activated alumina and pseudoboehmite;
  • P 2 0 5 is derived from phosphoric acid .
  • the templating agent in the present invention is one of triethylamine and diethylamine, or a mixture of two.
  • crystallization conditions of the SAPO-34 molecular sieve selected by the invention to control the synthesis of Si(4Al) as the main coordination environment are: crystallization temperature is 100-250 ° C; crystallization time is 2-120 hours.
  • the SAPO-34 molecular sieve rich in Si(4Al) structure means SAPO-34 molecular sieve having a Si(4Al) structure content of 70 to 100%.
  • the invention is described in detail below by way of examples.
  • silica sol 20.6 g of phosphoric acid, 13.6 g of pseudoboehmite and 68.3 g of H 2 0 were mixed and stirred to obtain a first gel mixture.
  • 30.3 g of TEA TEA is triethylamine
  • the second gel mixture was placed in a stainless steel synthesizer lined with polytetrafluoroethylene, sealed and heated to a sealed heat of 200 ° C, and subjected to constant temperature crystallization under autogenous pressure for 12 hours.
  • the sample No. SP34-1 and SP34-2 obtained in Example 1 were subjected to 29 Si solid nuclear magnetic characterization, and the molecular sieve skeleton Si coordination environment was measured. The results are shown in Fig. 2.
  • Comparative Example 1 was obtained with the number SP4-3; the SP4-4 sample was subjected to 29 Si solid nuclear magnetic characterization, and the molecular sieve skeleton Si coordination environment was measured. The results are shown in Fig. 2.
  • the molecular sieve framework Si SP34-3 ligand gel Si0 2 Al 2 0 3 molar ratio of / is synthesized with 0.20 Si (4Al) and Si (3Al) structure, its skeleton Si / Al molar ratio of 0.12; and when condensable
  • the synthesized Si344 molecular sieve skeleton Si has a structure of Si(4Al)Si(3Al)Si(2Al), Si(lAl) and Si(OAl).
  • the skeleton Si/Al molar ratio was 0.19.
  • the sample No. SP34-1, SP34-2 obtained in Example 1 was calcined at 550 ° C for 4 hours to obtain a SAPO-34 molecular sieve catalyst for methanol to olefin catalytic reaction.
  • 0.6 g of a sample of 20-40 mesh particulate catalyst was separately charged into a reactor, activated by nitrogen at 550 ° C for 1 hour, and then cooled to 450 ° C for reaction.
  • Nitrogen was used as a diluent gas to carry the raw material methanol, the nitrogen flow rate was 40ml/min, and the methanol weight space velocity was 2.011.
  • the composition of the material was analyzed by on-line gas chromatography, and the results are shown in Table 1.
  • the sample No. 1 obtained in Comparative Example 1 was SP34-3, and the sample of SP34-4 was calcined at 550 ° C for 4 hours to obtain a SAPO-34 molecular sieve catalyst for methanol-to-olefin catalytic reaction.
  • a sample of 0.6 g of a 20-40 mesh particle catalyst was separately charged into the reactor, activated by nitrogen at 550 ° C for 1 hour, and then cooled to 450 ° C for reaction.
  • the raw material methanol was carried with nitrogen as a diluent gas, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity 2.011 was analyzed by on-line gas chromatography. The results are shown in Table 2.

Abstract

Procédé de synthèse d'un tamis moléculaire SAPO-34 enrichi avec une structure Si(4AI) dans le squelette dans lequel l'environnement de coordination de Si est constitué par une structure Si(4AI9 dans le squelette du tamis moléculaire. Le processus de synthèse permet de contrôler la forme et le volume de l'environnement de coordination de Si en jouant sur le rapport d'adjonction de silicium dans le gel initial pour synthèse, ce qui permet de synthétiser un tamis moléculaire SAP0.34 ayant principalement un environnement de coordination Si(4AI). Le tamis moléculaire est utilisé comme catalyseur après étuvage et peut permettre d'améliorer efficacement la sélectivité de l'éthélène et du propène.
PCT/CN2007/002333 2006-08-08 2007-08-03 Procédé de synthèse d'un tamis moléculaire sapo-34 enrichi avec une structure si(4ai) dans le squelette WO2008019584A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN200610089178 2006-08-08
CN200610089178.3 2006-08-08
CN200610153083.3 2006-09-21
CN2006101530833A CN101121530B (zh) 2006-08-08 2006-09-21 骨架富含Si(4Al)结构的SAPO-34分子筛合成方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276398A (zh) * 2010-06-11 2011-12-14 中国石油化工股份有限公司 以甲醇为原料生产低碳烯烃的方法
CN102336413B (zh) * 2010-11-29 2013-04-17 中国科学院大连化学物理研究所 一种低硅sapo-34分子筛的合成方法
CN102557072B (zh) * 2010-12-29 2013-09-04 中国科学院大连化学物理研究所 Sapo-34分子筛的溶剂热合成方法和由其制备的催化剂
CN102530987A (zh) 2010-12-29 2012-07-04 中国科学院大连化学物理研究所 Sapo分子筛的溶剂热合成方法及由其制备的催化剂
CN108566593A (zh) * 2018-01-17 2018-09-21 瑞声科技（南京）有限公司 一种吸音材料及其制备方法和应用该吸音材料的扬声器
CN108275696A (zh) * 2018-01-04 2018-07-13 瑞声科技(新加坡)有限公司 一种分子筛、包括该分子筛的扬声器箱及该分子筛的制备方法
CN108314056B (zh) * 2018-05-18 2021-06-15 山西大同大学 选择性合成sapo-15和sapo-34分子筛的方法

Citations (2)

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US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
CN1596221A (zh) * 2001-11-29 2005-03-16 埃克森美孚化学专利公司 硅铝磷酸盐分子筛的生产方法

Patent Citations (2)

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US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
CN1596221A (zh) * 2001-11-29 2005-03-16 埃克森美孚化学专利公司 硅铝磷酸盐分子筛的生产方法

Non-Patent Citations (1)

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Title
LIU H. ET AL.: "Effects of Silicon Source Content and Crystallization Time on the Structure and Catalytic Performance of SAPO-34 Molecular Sieve", CHINESE JOURNAL OF INORGANIC CHEMISTRY, vol. 19, no. 3, March 2003 (2003-03-01), pages 240 - 245 *

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