WO2008019580A1 - Tamis moléculaire à micropores modifié par phosphore de silicoaluminium phosphate, son procédé de fabrication et son utilisation - Google Patents

Tamis moléculaire à micropores modifié par phosphore de silicoaluminium phosphate, son procédé de fabrication et son utilisation Download PDF

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Publication number
WO2008019580A1
WO2008019580A1 PCT/CN2007/002310 CN2007002310W WO2008019580A1 WO 2008019580 A1 WO2008019580 A1 WO 2008019580A1 CN 2007002310 W CN2007002310 W CN 2007002310W WO 2008019580 A1 WO2008019580 A1 WO 2008019580A1
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WO
WIPO (PCT)
Prior art keywords
molecular sieve
phosphorus
sapo
modified
phosphosilica
Prior art date
Application number
PCT/CN2007/002310
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English (en)
Chinese (zh)
Inventor
Peng Tian
Zhongmin Liu
Lixin Yang
Lei Xu
Cuiyu Yuan
Yue Yang
Original Assignee
Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 WO2008019580A1 publication Critical patent/WO2008019580A1/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
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the invention relates to a phosphorus modification method for a small pore phosphosilica molecular sieve, and a catalytic application of the molecular sieve catalyst prepared by the method for the conversion of an oxygenate to a low carbon olefin.
  • Low-carbon olefins are the basic raw materials for petrochemicals. With the development of the world economy, its demand is increasing year by year. The main route for the production of ethylene and propylene is currently through naphtha cracking. Because petroleum is a non-renewable resource with limited reserves, research and development of new low-carbon olefin production technologies is of great significance. Natural gas or coal by methanol The production of low-carbon olefins such as ethylene and propylene is the most promising alternative to the naphtha route to olefins.
  • SAPO-n phosphosilicate series molecular sieve
  • SAPO molecular sieves are a class of crystalline silicoaluminophosphates composed of tetrahedrons of P0 4 +, A10 4 — and Si0 4 . With the advent of silicoaluminophosphate series molecular sieves, SAPO molecular sieves with small pores and moderate acidity have been used for MTO reactions, such as SAPO-17, SAPO-18, SAPO-34, SAPO-44, etc. (US4499327). It is about 0.43 nm and is a good type of shape-selective catalyst.
  • SAPO-34 molecular sieve has become a hot spot in current research because of its excellent acidity and pore structure and excellent catalytic performance in MTO reaction.
  • Using SAPO-34 molecular sieve as catalyst in 1995 UOP Company of Norway and Norsk Hydro Company of Norway completed the MTO fluidized bed pilot test for 0.5 t / d methanol.
  • the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences completed the synthesis gas. Pilot test for the preparation of light olefins via dimethyl ether.
  • CN102247 reports the preparation of zeolite-catalyst (ZSM-5) modified with phosphorus-rare earth and its application in the process of toluene disproportionation and toluene and ethylene thiolation.
  • ZSM-5 zeolite catalyst modified with phosphorus and used for the alkylation of methyl styrene to obtain p-toluene, so that the isomer of p-toluene is up to 96% or more.
  • CN1176752 reports a method for catalyzing the catalytic activity of zeolite molecular sieves for catalytic cracking reaction, that is, adding phosphorus and rare earth compounds to zeolite molecular sieves, reacting at room temperature for a period of time, filtering and drying to obtain modified products.
  • CN1704167 provides a catalyst for zeolite Row modification to increase the selectivity to para-xylene in the methylation reaction of toluene.
  • the method comprises: forming a slurry of an aqueous solution of ZSM-5 zeolite and a phosphorus compound; removing water from the slurry to provide a non-steam treated, phosphorus-treated ZSM-5 zeolite catalyst without passing through an organic phosphorus vapor Deposited on the catalyst.
  • W09928277 reports an oxygen-containing chelate reagent for treating small pore molecular sieves.
  • the modified molecular sieve is used as a catalyst for the conversion of oxygenates to olefins, which can effectively reduce the selectivity of formazan.
  • the object of the present invention is to provide a phosphorus modification method for a small pore phosphosilica molecular sieve, which comprises mixing an inorganic phosphorus or an organic phosphine-containing compound with a small-porous phosphosilica molecular sieve raw powder by a dipping method to prepare a modified molecular sieve.
  • the present invention is characterized in that the small pore phosphosilicate aluminum molecular sieve used is one or a mixture of SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-35, SAPO-56.
  • the phosphorus modification method of the present invention is prepared as follows:
  • the compound containing the organic phosphine is dissolved in an organic solvent (such as ethanol or toluene, etc.), and the molecular sieve raw powder is impregnated at room temperature for 1-24 hours ;
  • the modified small pore SAPO molecular sieve obtained in the step b) is dried at 80 to 120 ° C, and calcined in air at 500-700 ° C for 3 to 8 hours to obtain a modified SAPO molecular sieve catalyst.
  • the inorganic phosphorus-containing compound of the present invention is one or a mixture of orthophosphoric acid and soluble phosphate.
  • the organic phosphine-containing compound of the present invention is a mixture of one or more of an organic phosphine or a phosphine oxide.
  • the phosphorus-modified small-porosity silicalite molecular sieve of the present invention has a mass content of phosphorus of 0.1 to 5% increased in the sample obtained by calcination.
  • the modified molecular sieve catalyst obtained by the invention can be applied to the conversion of an oxygenate to an olefin, and the modified molecular sieve has an initial selectivity to the lower olefin of the unmodified molecular sieve.
  • the modified SAPO-34 molecular sieve catalyst obtained in Example 1-3 was used for methanol to olefin catalytic reaction, and the unmodified SAPO-34 molecular sieve raw powder was calcined in air for 600 hours, and the organic template was completely removed.
  • Nitrogen was used as a diluent gas to carry the raw material methanol, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity lOl ⁇ reaction product composition was analyzed by on-line gas chromatography. The results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Tamis moléculaire à micropores modifié par phosphore de silicoaluminium phosphate, son procédé de fabrication et son utilisation. Ce procédé consiste à mélanger la poudre du tamis moléculaire de silicoaluminium phosphate, tel que SAPO-34, avec un composé de phosphore inorganique ou phosphine selon un procédé d'immersion. Le tamis moléculaire modifié, qui peut s'utiliser comme catalyseur pour transformer une charge de composé oxygéné en oléfines, présente pour les oléfines à faible teneur en carbone une sélectivité supérieure à celle de tamis moléculaires non modifiés.
PCT/CN2007/002310 2006-08-08 2007-07-31 Tamis moléculaire à micropores modifié par phosphore de silicoaluminium phosphate, son procédé de fabrication et son utilisation WO2008019580A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN200610089169 2006-08-08
CN200610089169.4 2006-08-08
CN200610160684.7 2006-12-04
CNA2006101606847A CN101121531A (zh) 2006-08-08 2006-12-04 一种小孔磷硅铝分子筛的磷改性方法

Publications (1)

Publication Number Publication Date
WO2008019580A1 true WO2008019580A1 (fr) 2008-02-21

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PCT/CN2007/002310 WO2008019580A1 (fr) 2006-08-08 2007-07-31 Tamis moléculaire à micropores modifié par phosphore de silicoaluminium phosphate, son procédé de fabrication et son utilisation

Country Status (2)

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CN (1) CN101121531A (fr)
WO (1) WO2008019580A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992349A (zh) * 2012-12-11 2013-03-27 陕西煤化工技术工程中心有限公司 一种sapo-34分子筛合成母液的循环利用方法
CN113526522A (zh) * 2020-04-13 2021-10-22 中国石油化工股份有限公司 磷改性mfi结构分子筛及其制备方法
CN114713277A (zh) * 2021-01-05 2022-07-08 中国石油化工股份有限公司 一种改性mfi结构硅铝分子筛及其制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101632939B (zh) * 2008-07-24 2015-07-29 中国石油化工股份有限公司 一种含磷酸硅铝分子筛的组合物、制备方法及其应用
CN101633509B (zh) * 2008-07-24 2012-02-29 中国石油化工股份有限公司 一种磷酸硅铝分子筛的改性方法
CN103566967B (zh) * 2012-08-03 2016-01-20 中国石油化工股份有限公司 一种烯烃异构化催化剂及其制备方法
CN103769208B (zh) * 2012-10-24 2016-08-03 中国石油化工股份有限公司 一种磷改性的sapo-11分子筛催化剂及其制备方法和应用
CN106064823A (zh) * 2016-05-30 2016-11-02 中国天辰工程有限公司 一种改性sapo‑34分子筛的方法
CN109647503B (zh) * 2017-10-10 2021-11-16 中国石油化工股份有限公司 一种由合成气制备低碳烯烃的复合催化剂及其制备方法和由合成气制备低碳烯烃的方法
CN110801862A (zh) * 2019-10-24 2020-02-18 杜成荣 一种甲醇制备低碳烯烃的催化剂

Citations (4)

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US4605637A (en) * 1983-02-14 1986-08-12 Mobil Oil Corporation Hydrothermal activation of acid zeolites with aluminum phosphates
US5378670A (en) * 1993-04-16 1995-01-03 W. R. Grace & Co.-Conn. Phosphorus zeolites/molecular sieves
CN1291915A (zh) * 1998-03-11 2001-04-18 埃克森化学专利公司 用磷酸铝和磷提高沸石催化剂的活性
US20060106270A1 (en) * 2004-11-12 2006-05-18 Glover Bryan K Selective conversion of oxygenate to propylene using moving bed technology and a hydrothermally stabilized dual-function catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4605637A (en) * 1983-02-14 1986-08-12 Mobil Oil Corporation Hydrothermal activation of acid zeolites with aluminum phosphates
US5378670A (en) * 1993-04-16 1995-01-03 W. R. Grace & Co.-Conn. Phosphorus zeolites/molecular sieves
CN1291915A (zh) * 1998-03-11 2001-04-18 埃克森化学专利公司 用磷酸铝和磷提高沸石催化剂的活性
US20060106270A1 (en) * 2004-11-12 2006-05-18 Glover Bryan K Selective conversion of oxygenate to propylene using moving bed technology and a hydrothermally stabilized dual-function catalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992349A (zh) * 2012-12-11 2013-03-27 陕西煤化工技术工程中心有限公司 一种sapo-34分子筛合成母液的循环利用方法
CN113526522A (zh) * 2020-04-13 2021-10-22 中国石油化工股份有限公司 磷改性mfi结构分子筛及其制备方法
CN113526522B (zh) * 2020-04-13 2023-02-21 中国石油化工股份有限公司 磷改性mfi结构分子筛及其制备方法
CN114713277A (zh) * 2021-01-05 2022-07-08 中国石油化工股份有限公司 一种改性mfi结构硅铝分子筛及其制备方法
CN114713277B (zh) * 2021-01-05 2023-07-14 中国石油化工股份有限公司 一种改性mfi结构硅铝分子筛及其制备方法

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