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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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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molecular sieve
phosphorus
sapo
modified
phosphosilica
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Peng Tian
Zhongmin Liu
Lixin Yang
Lei Xu
Cuiyu Yuan
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
    • 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.

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  • 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)

Description

磷改性的小孔磷硅铝分子筛、其制备方法和其用途 技术领域
本发明涉及一种小孔磷硅铝分子筛的磷改性方法， 及釆用该方法制备的分子筛催 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， 人们开始将小孔且酸性适 中的 SAPO分子筛用于 MTO反应， 如 SAPO-17, SAPO-18, SAPO-34, SAPO-44等 (US4499327) o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， 中国科学院 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和选择性 是一种常用的手段。 如 CN102247报道了用磷一稀土改性的沸石催化剂 （ZSM-5 ) 的 制备方法及在甲苯歧化和甲苯、 乙烯垸基化反应过程中的应用。 CN1001768发明了一 种用磷改性的 ZSM-5沸石催化剂，并用于甲苯乙烯烷基化制取对甲乙苯，使产物中对 甲乙苯异构体高达 96%以上。 CN1176752报道了一种适用于提髙用于催化裂化反应过 程的沸石分子筛催化活性的方法， 即在沸石分子筛中加入磷和稀土化合物， 室温下反 应一段时间， 过滤， 干燥即可制得改性产品。 CN1704167提供了一种对沸石催化剂进 行改性以增加在甲苯甲基化反应中对二甲苯选择性的方法。该方法包括： 形成 ZSM-5 沸石和磷化合物的水溶液的淤浆； 从淤浆中除去水， 提供一种未经蒸汽处理的、 经磷 处理的 ZSM-5沸石催化剂， 而无需通过有机磷蒸汽沉积在催化剂上。 W09928277报 道了一种含氧螯合物试剂处理小孔分子筛的方法， 修饰后的分子筛用作含氧化合物转 化制烯烃反应的催化剂， 可以有效降低甲垸的选择性。
到目前为止， 还未见到关于小孔磷硅铝分子筛原粉进行磷改性， 并用于含氧化合 物转化反应的报道。 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磷改性方法，在于采用浸渍法将 含无机磷或有机膦的化合物与小孔磷硅铝分子筛原粉混合， 制备改性分子筛。
本发明的特点在于使用的小孔磷硅铝分子筛为 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。 本发明的磷改性方法， 制备过程如下：
a) 水热合成小孔 SAPO分子筛， 100〜12(TC烘干， 得分子筛原粉；
b) 引入磷元素- 将含有无机磷的磷酸或可溶性磷盐的水溶液浸渍分子筛原粉， 浸渍时间 l-24h， 浸渍温度 0-90Ό ; 或
将含有有机膦的化合物溶于有机溶剂 （如乙醇或甲苯等）， 并常温下浸渍分子筛 原粉， 浸渍时间 l-24h;
c) 将步骤 b)中得到的改性小孔 SAPO分子筛在 80〜120°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。 本发明的含无机磷化合物为正磷酸、 可溶型磷酸盐中的一种或几种的混合物。 本发明的含有机膦化合物为有机膦化物或膦氧化物中的一种或几种的混合物。 本发明所述的磷改性的小孔磷硅铝分子筛经焙烧后得到的样品中所含磷的质量 含量增加 0.1〜5%。 本发明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 子筛比未改性分子筛的低碳烯烃初始选择性髙。 具体实施方式
下面通过实施例详述本发明。 实施例 1
配制 0.3mOl/L的磷酸水溶液， 然后采用等体积浸渍的方法与 lg SAPO-34分子筛 原粉 (合成过程参见授权专利 CN1037334)混合均勾， 80DC浸渍 2h， 然后 120°C烘干， 600Ό空气中焙烧 4小时， 得到改性 SAPO-34分子筛催化剂， 记为 PSP34-1。 实施例 2
配制 0.5mol/L的磷酸二氢铵水溶液， 然后采用等体积浸渍的方法与 lg SAPO-34 分子筛原粉（合成过程参见授权专利 CN1037334)混合均匀，室温浸渍 24h，然后 120 °C烘干， 600°C空气中焙烧 4小时， 得到改性 SAPO-34分子筛催化剂， 记为 PSP34-2。 实施例 3
配制 0.5mol/L膦酸三乙酯的乙醇溶液，然后采用等体积浸渍的方法与 lg SAPO-34 分子筛原粉 (合成过程参见授权专利 CN1037334)混合均匀，室温浸渍 5h，然后 80°C烘 干， 60(TC空气中焙烧 4小时， 得到改性 SAPO-34分子筛催化剂， 记为 PSP34-3。
实施例 4
将实施例 1-3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 600Ό空气中焙烧 4小时，完全除去有机模板剂后也进 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 500°C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 lOl ^ 反应产物组成采用在线气相色谱分析， 结果如表 1所示。
可以看到， 经磷改性后的分子筛的甲醇转化制烯烃反应中低碳烯烃的初始选择性 明显增加。 P T/CN2007/002310 表 i甲醇转化制烯烃反应结果 *
Figure imgf000005_0001
产物分布
CH4 2.63 2.17 2.47 2.21
C2H4 42.67 44.64 44.38 45.51
C2H6 0.49 0.53 0.63 0.74
C3H6 37.91 39.13 39.44 39.07
C3H8 1.63 1.31 1.65 1.19
C4+ 10.29 9.17 8.16 8.59
C5+ 3.62 2.63 2.83 2.35
C6+ 0.75 0.42 0.44 0.35
∑C2 =-C3 = 80.58 83.77 83.82 84.58
* 反应时间 2min,转化率均为 100%。

Claims

1. 一种小孔磷硅铝分子筛的磷改性方法，其特征在于，所述方法包括采用浸渍法 将含无机磷或有机膦的化合物与小孔磷硅铝分子筛原粉混合， 制备改性分子筛的步 骤。
权
2. 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 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。 求
3.按照权利要求 1所述的方法， 其特征在于， 所述含无机磷的化合物为正磷酸、 可溶型磷酸盐中的一种或几种的混合物。
4.按照权利要求 1所述的方法，其特征在于，所述含有机膦的化合物为有机膦化 物或膦氧化物中的一种或几种的混合物。
5.按照权利要求 1所述的方法， 其特征在于， 如下进行所述混合步骤：将含无机 磷的化合物的水溶液浸渍分子筛原粉， 浸渍时间 l〜24h， 浸渍温度 0〜90'C ; 或将含 有机膦的化合物溶于有机溶剂， 并常温下浸渍分子筛原粉， 浸渍时间 l〜24h。
6. 按照权利要求 5所述的方法， 其特征在于， 所述有机溶剂为乙醇或甲苯。
7. 一种通过权利要求 1所述的方法制备的磷改性的小孔磷硅铝分子筛。
8.按照权利要求 7所述的磷改性的小孔磷硅铝分子筛，其特征在于，经焙烧后得 到的改性分子筛所含磷的质量含量增加 0.1〜5 %。
9. 按照权利要求 Ί所述的磷改性的小孔磷硅铝分子筛在催化含氧化合物转化制 低碳烯烃反应中的应用。
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 Ceased WO2008019580A1 (fr)

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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

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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
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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

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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
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