WO2008019585A1 - A method for modifying micropore molecular sieve of silicoaluminum phosphate by using metal - Google Patents

A method for modifying micropore molecular sieve of silicoaluminum phosphate by using metal Download PDF

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WO2008019585A1
WO2008019585A1 PCT/CN2007/002349 CN2007002349W WO2008019585A1 WO 2008019585 A1 WO2008019585 A1 WO 2008019585A1 CN 2007002349 W CN2007002349 W CN 2007002349W WO 2008019585 A1 WO2008019585 A1 WO 2008019585A1
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molecular sieve
modified
metal
sap0
sapo
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Peng Tian
Zhongmin Liu
Lei Xu
Lixin Yang
Yue Yang
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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)

Definitions

  • the invention relates to a metal modification method of a small pore phosphorus silicon aluminum molecular sieve, and a catalytic application of a metal modified molecular sieve catalyst in the reaction of converting oxygen compounds into low carbon olefins.
  • 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 .
  • 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 their pore sizes are approximately It is a good type of shape-selective catalyst with 0.43nm.
  • SAPO-34 molecular sieve has become a hot spot in MTO reaction due to its suitable acidity and pore structure.
  • CN1167654A discloses the modification of SAPO-34 by using Cu, Co, Ni, Ca, Ba or Sr, and adding a binder and a pore former to prepare a catalyst for converting methanol or dimethyl ether into a lower olefin.
  • the metal is introduced into the SAPO-34 molecular sieve by direct in situ synthesis or impregnation, and the mass of the metal in the molecular sieve is 0.01-0.15%.
  • CN1216941A reports the use of calcium, strontium and barium and mixtures thereof to modify small pore molecular sieves and their use in the conversion of oxygenates.
  • the modification method of the molecular sieve of the patent is divided into two types, one is direct in-situ synthesis, and the other is to modify the synthesized molecular sieve raw powder by the impregnation method.
  • US4752651 Non-zeolite small pore molecular sieves have been reported to be modified with alkaline earth metals strontium and magnesium.
  • JP 940 74 134 discloses a process for alkaline earth metal modified molecular sieves which refers to a molecular sieve pore size between macroporous zeolites such as X and Y zeolites and small pore molecular sieves such as erionite and chabazite.
  • US2004224839 reports a process for modifying calcined SAPO molecular sieves such as SAPO-34 using organometallic reagents. Summary of the invention
  • the technical solution of the present invention is to provide a metal modification method for a small-porous phosphosilica molecular sieve, which comprises impregnating or mechanically grinding a compound containing an alkali metal and/or a transition metal with a small hole.
  • the original powder of the phosphorus silicon aluminum molecular sieve is mixed to prepare a modified molecular sieve.
  • the small pore phosphosilica molecular sieve is one or a mixture of SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-35, and SAPO-56.
  • the alkali metal-containing source is one or a mixture of oxides, inorganic salts or organic salts of calcium, barium or strontium; the source of the transition metal is copper or zinc.
  • the modified molecular sieve prepared by the high-temperature calcination removal of the template has a mass content of 0.1-5 %.
  • the modified molecular sieve prepared by the high-temperature calcination removal of the templating agent has a metal content of 0.5-3%.
  • the preparation method is as follows: a) hydrothermal synthesis of small pores SAPO molecular sieve, drying at 100-120 ° C, to obtain molecular sieve raw powder;
  • modified small pore SAPO molecular sieve obtained in the step b) is dried at 120 ° C, and calcined in air at 500-700 ° C for 3-8 hours to obtain a modified SAPO molecular sieve catalyst.
  • the modified molecular sieve catalyst obtained by the method of the invention can be applied to the conversion of oxygenates to olefins, and the modified molecular sieves exhibit higher initial selectivity of lower olefins than unmodified molecular sieves.
  • the method of the invention adopts a method of impregnation or mechanical grinding to mix a compound containing an alkali metal (calcium, barium or strontium) and/or a transition metal (copper or zinc) with a small-porous phosphosilica molecular sieve raw powder (such as SAPO-34). Mixing, preparing modified molecular sieves.
  • a compound containing an alkali metal calcium, barium or strontium
  • a transition metal copper or zinc
  • the invention is characterized in that the small pore silicon aluminum molecular sieve used is one or a mixture of any one of SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-35, SAPO-56.
  • step b) The modified pores obtained in step b) are dried at 120 ° C and calcined in air at 500-700 ° C.
  • the modified SAPO molecular sieve catalyst was obtained in 3-8 hours.
  • the present invention is characterized in that the source of the metal used is one or a mixture of oxides, inorganic salts or organic salts of calcium, barium, strontium, copper or zinc. After the modified molecular sieve is calcined at a high temperature to remove the templating agent, the metal content thereof is 0.1-5%.
  • the invention is described in detail below by way of examples.
  • the modified SAPO-34 molecular sieve catalyst obtained in Example 1-4 was used for methanol to olefin catalytic reaction, and the unmodified SAPO-34 molecular sieve raw powder was calcined and the template was also calcined to evaluate the reaction.
  • Reaction conditions 2.5 g of a sample of 20-40 mesh granule catalyst was charged into a reactor, activated by nitrogen at 550 ° C for 1 hour, and then cooled to 50 (TC was carried out. The nitrogen was used as a diluent gas to carry the raw material methanol, nitrogen flow rate The molecular weight of the methanol was 2.01 ⁇ at 40 ml/min.
  • the composition of the reaction product was analyzed by on-line gas chromatography, and the results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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Description

一种小孔磷硅铝分子筛的金属改性方法
技术领域
本发明涉及一种小孔磷硅铝分子筛的金属改性方法， 及金属改性分子筛催化剂在 含氧化合物转化制低碳烯烃反应中的催化应用。 背景技术
低碳烯烃是石油化工的基础原料。 随着世界经济的发展，其需求呈逐年增加的趋 势。 目前制取乙烯、 丙烯的主要路线是通过石脑油裂解。 由于石油是不可再生的资源 且储藏量有限，因此研究和开发新的低碳烯烃生产技术具有重要的意义。 天然气或煤经 由甲醇制乙烯、丙烯等低碳烯烃是最有希望替代石脑油路线制烯烃的工艺。天然气（或 煤） 制取甲醇的单系列、 大规模工业化的技术已十分成熟， 所以由甲醇制取烯烃的研 究成为非石油路线制取低碳烯烃的关键技术。
1984年， 美国联合碳化物公司 （UCC) 开发了新型磷硅铝系列分子筛 （SAPO-n)
(USP 4440871)。 SAPO分子筛是一类结晶硅铝磷酸盐， 由 P04+、 A104—、 及 Si04的四 面体构成三维骨架结构。 随着磷酸硅铝系列分子筛的问世， 人们幵始将小孔且酸性适 中的 SAPO分子筛用于 MTO反应， 如 SAPO-17， SAPO-18, SAPO-34, SAPO-44等 (US4499327 它们的孔径大约为 0.43nm， 是一类较好的择形催化剂。其中 SAPO-34 分子筛由于具有适宜的酸性和孔道结构在 MTO 反应中呈现出优异的催化性能， 成为 当前研究的热点。 以 SAPO-34分子筛为催化剂， 1995年美国 UOP公司与挪威 Norsk Hydro公司完成了处理 0.5 t / d甲醇的 MTO流化床中试试验， 在同一年， ψ国科学院 大连化学物理研究所完成了合成气经由二甲醚制取低碳烯烃的中试试验。
在以分子筛作为催化剂的反应中， 对分子筛改性以提高催化反应的活性、 选择性 是一种常用的手段。如 CN1167654A公布了使用 Cu、 Co、 Ni、 Ca、 Ba或 Sr对 SAPO-34 进行改性， 同时加入粘结剂和造孔剂制备甲醇或二甲醚转化为低碳烯烃的催化剂。 金 属通过直接原位合成或浸渍的方法引入到 SAPO-34分子筛中，金属在分子筛中的质量 含量为 0.01-0.15 %。 CN1216941A报道了使用钙、锶和钡及其混合物对小孔分子筛进 行改性的方法及它们在含氧化合物转化中的应用。 该专利对分子筛的改性方法分为两 种，一为直接原位合成,二为采用浸渍法对合成后的分子筛原粉进行改性。 US4752651 报道了用碱土金属铍和镁对非沸石的小孔分子筛进行改性。 JP94074134公布了碱土金 属改性分子筛的方法，其所指的分子筛孔径介于大孔沸石如 X和 Y型沸石和小孔分子 筛如毛沸石和菱沸石之间。 US2004224839报道了采用有机金属试剂修饰焙烧型 SAPO 分子筛如 SAPO-34的方法。 发明内容
本发明的目的在于提供一种小孔磷硅铝分子筛的金属改性方法。
为达到上述目的， 本发明的技术解决方案是提供一种小孔磷硅铝分子筛的金属改 性方法， 其采用浸渍法或机械研磨的方法将含碱金属和 /或过渡金属的化合物与小孔磷 硅铝分子筛原粉混合， 制备改性分子筛。
所述的方法，其所述小孔磷硅铝分子筛为 SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-35, SAPO-56其中的一种或任意几种的混合物。
所述的方法， 其所述含碱金属的来源为钙、 锶或钡的氧化物、 无机盐类或有机盐 类中的一种或任意几种的混合物； 过渡金属的来源为铜或锌的氧化物、 无机盐类或有 机盐类中的一种或任意几种的混合物。
所述的方法， 其制备的改性分子筛经高温焙烧除模板剂后， 其中所含金属的质量 含量为 0.1-5 % .
所述的方法， 其制备的改性分子筛经高温焙烧除模板剂后， 其中所含金属的质量 含量为 0.5-3%。
所述的方法， 其制备过程如下- a) 水热合成小孔 SAPO分子筛， 100-120°C烘干， 得分子筛原粉；
b) 引入改性金属：
1 ) 采用浸渍法， 将含有改性金属离子的可溶性盐溶液浸渍分子筛原粉， 常 温下浸渍 l-24h;
2) 或采用机械研磨的方法， 将含有改性金属的化合物与分子筛原粉混合， 研磨至均匀为止；
c) 将步骤 b)中得到的改性小孔 SAPO分子筛在 120°C烘干， 500-700°C空气中焙 烧 3-8小时， 得改性 SAPO分子筛催化剂。
本发明方法得到的改性分子筛催化剂可以应用于含氧化合物转化制烯烃反应， 改 性分子筛显示了比未改性分子筛高的低碳烯烃初始选择性。 具体实施方式
本发明方法是采用浸渍法或机械研磨的方法， 将含碱金属 （钙、 锶或钡）和 /或过 渡金属 （铜或锌） 的化合物与小孔磷硅铝分子筛原粉 （如 SAPO-34) 混合， 制备改性 分子筛。
本发明的特点在于使用的小孔憐硅铝分子筛为 SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-35, SAPO-56中的一种或任意几种的混合物。
本发明的特点在于制备过程如下:
a)水热合成小孔 SAPO分子筛， 100-1201烘¥， 得分子筛原粉；
b)引入改性金属
i. 采用浸渍法， 将含有改性金属离子的可溶性盐溶液浸渍分子筛原粉， 浸渍时间 l-24h;
ii. 采用机械研磨的方法， 将含有改性金属的化合物与分子筛原粉混合， 研磨至均匀为止；
c)将步骤 b)中得到的改性小孔 SAPO分子筛在 120°C烘干， 500-700'C空气中焙烧
3-8小时， 得改性 SAPO分子筛催化剂。
本发明的特点在于所使用金属的来源为钙、 锶、 钡、 铜或锌等的氧化物、 无机盐 类或有机盐类中的一种或任意几种的混合物。 改性分子筛经高温焙烧除模板剂后， 其 中所含金属的质量含量为 0.1-5%。 下面通过实施例详述本发明。 实施例 1
将 0.5gSr(NO3)2溶于适量去离子水， 然后将含锶的水溶液与 12.5g SAPO-34 分子筛原粉 (合成方法见专利 CN1131845)混合均匀， 室温浸渍 2h, 然后 120 'C烘 干， 600°C空气中焙烧 3-8 小时， 得到锶改性的 SAPO-34 分子筛催化剂， 记为 GSP34-1。 实施例 2
将 0.68gZn(NO3)2.6H2O 溶于适量去离子水， 然后将含锌的水溶液与 12.5g SAPO-34分子筛原粉 （同实施例 1 ) 混合均匀， 室温浸渍 2h, 然后 120'C烘干， 500°C空气中焙烧 3-8小时，得到锌改性的 SAPO-34分子筛催化剂，记为 GSP34-2。 实施例 3
将 0.25gSr(NO3)2和 0.24gCu(C2H3O2)2溶于适量去离子水， 然后将含金属的水 溶液与 12.5g SAPO-34分子筛原粉 （同实施例 1 ) 混合均匀， 室温浸渍 2h， 然后 120°C烘干， 500'C空气中焙烧 3-8小时， 得到锶和铜同时改性的 SAPO-34分子筛 催化剂， 记为 GSP34-3。 实施例 4
将 0.68gZn(NO3)2.6H2O与 12.5g SAPO-34分子筛原粉 （同实施例 1 ) 混合均 匀， 机械研磨使得两相混合均匀， 然后 600°C空气中焙烧 3-8小时， 得到锌改性的 SAPO-34分子筛催化剂， 记为 GSP34-4。 实施例 5
将实施例 1-4得到的改性 SAPO-34分子筛催化剂用于甲醇制烯烃催化反应， 同时未改性的 SAPO-34分子筛原粉焙烧除模板剂后也进行了反应评价。 反应条 件： 2.5克 20-40目的颗粒催化剂样品， 装入反应器中， 在 550°C下通氮气活化 1 小时， 然后降温至 50(TC进行反应。 以氮气为稀释气携带原料甲醇， 氮气流速为 40ml/min, 甲醇重量空速 2.01^。 反应产物组成采用在线气相色谱分析， 结果如 表 1所示。
表 1甲醇转化制烯烃反应结果 *
Figure imgf000006_0001
产物分布
CH4 2.05 1.93 2.18 2.06 1.83
C2H4 41.94 44.82 45.45 45.03 45.80
C2 0.28 0.32 0.24 0.39 0.30
C3H6 38.89 38.95 38.63 38.33 38.46
C3H8 1.58 1.18 1.10 1.48 1.19
C4+ 11.16 9.66 9.06 9.40 9.47 cs+ 3.52 3.14 3.10 3.04 2.93 c6+ 0.59 - 0.25 0.27 -
∑c2=-c3= 80.83 83.77 84.05 83.36 84.26
* 反应时间 2min, 转化率均为 100%。

Claims

权 利 要 求
、 一种小孔磷硅铝分子筛的金属改性方法，其特征在于，采用浸渍法或机械研磨的方 法将含碱金属和 /或过渡金属的化合物与小孔磷硅铝分子筛原粉混合， 制备改性分 子筛。 、 按照权利要求 1 所述的方法， 其特征在于， 所述小孔磷硅铝分子筛为 SAP0-17, SAP0-18, SAPO-34, SAP0- 44， SAP0-35, SAP0- 56其中的一种或几种的混合物。 、 按照权利要求 1所述的方法， 其特征在于， 所述含碱金属的来源为钙、锶或钡的氧 化物、无机盐类或有机盐类中的一种或任意几种的混合物；过渡金属的来源为铜或 锌的氧化物、 无机盐类或有机盐类中的一种或几种的混合物。 、 按照权利要求 1所述的方法，其特征在于， 制备的改性分子筛经高温焙烧除模板剂 后， 其中所含金属的质量含量为 0. 1-5%。 、 按照权利要求 1所述的方法，其特征在于，制备的改性分子筛经高温焙烧除模板剂 后， 其中所含金属的质量含量为 0. 5-3%。 、 按照权利要求 1所述的方法， 其特征在于， 包括以下步骤- a) 水热合成小孔 SAP0分子筛， 100-120Ό烘干， 得分子筛原粉；
b) 引入改性金属：
1 ) 采用浸渍法，将含有改性金属离子的可溶性盐溶液浸渍分子筛原粉， # 温下浸渍 1- 24h;
2) 釆用机械研磨的方法，将含有改性金属的化合物与分子筛原粉混合，研 磨至均匀为止；
c) 将步骤 b ) 中得到的改性小孔 SAP0分子筛在 120Ό烘干， 500-700Ό空气中焙 烧 3- 8小时， 得改性 SAP0分子筛催化剂。
6
替换页（细则第 26条)
PCT/CN2007/002349 2006-08-08 2007-08-06 A method for modifying micropore molecular sieve of silicoaluminum phosphate by using metal Ceased WO2008019585A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1167654A (zh) * 1996-06-07 1997-12-17 中国科学院大连化学物理研究所 金属改性小孔磷硅铝型分子筛催化剂及其制备方法和应用
CN1207722A (zh) * 1995-12-13 1999-02-10 埃克森化学专利公司 含过渡金属的小孔分子筛催化剂在含氧化合物转化中的应用
CN1216941A (zh) * 1996-04-04 1999-05-19 埃克森化学专利公司 含碱土金属的非沸石的小孔分子筛催化剂在含氧化合物转化中的应用
CN1754624A (zh) * 2004-09-28 2006-04-05 中国石油化工股份有限公司 一种金属改性的sapo－34分子筛及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1207722A (zh) * 1995-12-13 1999-02-10 埃克森化学专利公司 含过渡金属的小孔分子筛催化剂在含氧化合物转化中的应用
CN1216941A (zh) * 1996-04-04 1999-05-19 埃克森化学专利公司 含碱土金属的非沸石的小孔分子筛催化剂在含氧化合物转化中的应用
CN1167654A (zh) * 1996-06-07 1997-12-17 中国科学院大连化学物理研究所 金属改性小孔磷硅铝型分子筛催化剂及其制备方法和应用
CN1754624A (zh) * 2004-09-28 2006-04-05 中国石油化工股份有限公司 一种金属改性的sapo－34分子筛及其应用

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