WO2020156423A1 - 一种乙烯乙烷的分离方法 - Google Patents

一种乙烯乙烷的分离方法 Download PDF

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WO2020156423A1
WO2020156423A1 PCT/CN2020/073769 CN2020073769W WO2020156423A1 WO 2020156423 A1 WO2020156423 A1 WO 2020156423A1 CN 2020073769 W CN2020073769 W CN 2020073769W WO 2020156423 A1 WO2020156423 A1 WO 2020156423A1
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ethylene
ethane
adsorption
ultra
anion
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邢华斌
张照强
崔希利
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Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives

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  • the invention belongs to the technical field of chemical separation, and specifically relates to an anion hybrid ultra-microporous material used for the separation of ethylene and ethane.
  • ethylene is mainly derived from natural gas and petroleum hydrocarbon cracking. It is one of the largest chemical products in the world.
  • the ethylene industry is the core of the petrochemical industry. Ethylene products account for more than 75% of petrochemical products.
  • Ethylene is mainly used to produce polyethylene, ethylene-propylene rubber and other polymers, and it needs to reach high purity during the utilization process.
  • ethane can be used as the main raw material for steam cracking to produce ethylene, which has a high demand.
  • the main processes for industrial ethylene and ethane separation include cryogenic separation, absorption separation and adsorption separation.
  • the cryogenic separation method mainly uses cryogenic rectification, which often requires higher pressure and extremely low temperature (-160°C) to pass the raw materials.
  • the difference in the volatility of each component in the ethylene and ethane achieves separation, while the relative volatility of ethylene/ethane is small, and the number of rectification tower plates is usually greater than 100, which makes the process high energy consumption, large investment, and complex process. Therefore, it is extremely urgent to develop an efficient, energy-saving and environmentally friendly ethylene and ethane separation method.
  • the adsorption separation method mainly uses porous adsorbents to achieve ethylene/ethane separation under normal temperature and pressure, and has the advantages of low energy consumption, low cost, and simple operation process, and has good industrial application prospects.
  • the core is to choose a good adsorbent.
  • the ideal adsorbent should have the characteristics of large adsorption capacity, large separation factor and long service life.
  • molecular sieves or porous material adsorbents currently used have low adsorption capacity or low selectivity.
  • the invention provides a separation method of ethylene and ethane, which realizes the selective recognition of ethylene, and can also realize the selective separation of ethylene and ethane through the dynamic diffusion rate, and can obtain high-purity ethylene and ethane (99.99%).
  • a method for separating ethylene and ethane including the following steps: contacting a mixed gas of ethylene and ethane with an ultramicroporous anion pillared hybrid material to selectively adsorb ethylene molecules to separate ethylene and ethane;
  • the general expression of the ultra-microporous anion pillared hybrid material is [L 2 -MA] n , which is constructed by organic ligands L, inorganic fluorine-containing anions A and metal ions M through coordination bonds, where n is A positive integer, which means that the ultra-microporous anionic pillared hybrid material is composed of several structural units composed of L 2 -MA arranged regularly;
  • the organic ligand L is pyrazine
  • the inorganic fluorine-containing anion A is any one of SiF 6 2- , GeF 6 2- , TiF 6 2- , SnF 6 2- , and NbF 6 - ;
  • the metal ion M is any one of Fe 2+ , Co 2+ , and Ni 2+ .
  • the preparation method of the ultra-microporous anion pillared hybrid material is to simply mix the raw materials, then 1) use methanol and water as the solvent, stir the reaction, and then vacuum dry to obtain or 2) after high-speed collision grinding by a ball mill, methanol wash and dry. Got.
  • the ultra-microporous anion pillared hybrid material constructed by the above-mentioned organic ligand L, inorganic fluorine-containing anion A and metal ion M through coordination bonds has a one-dimensional pipeline pore structure with a pore diameter of The pore size of the material is the distance between two diagonally opposite F atoms in the channel.
  • the pore structure and material coordination structure of the ultra-microporous anion pillared hybrid material are shown in Figure 11, and are composed of several structural units regularly arranged:
  • the arrangement of the three in a single structural unit is: four organic ligands are connected to form a square frame through four metal end points, inorganic anions are connected to the metal ion end points through coordination bonds, and the inorganic anion is connected to another structural unit to form a three-dimensional frame structure.
  • the structural units are arranged in sequence along the axial direction to form a one-dimensional pipe-type pore structure (that is, one of the pores in Figure 11), and the one-dimensional pipe-type pores are arranged in a radial direction to form a multi-channel hybrid material (Figure 11 is four Arrangement diagram of one-dimensional pipe-type channels).
  • the anionic hybrid ultra-microporous material used in the present invention is constructed from pyrazine organic ligands, metal ions and inorganic fluorine-containing anions through coordination bonds.
  • the pore size is The material has one-dimensional pores, and each pore unit contains 4 anions. Through pore size limitation, anion selective recognition and kinetic diffusion difference, the selective adsorption and separation of ethylene/ethane can be achieved.
  • the anionic hybrid ultra-microporous material is [L 2 -Fe-A] n , in which the metal ion is Fe 2+ ; it can realize the thermodynamic separation of ethylene/ethane mixed gas, and can also realize ethylene/ethane mixed gas The kinetic separation;
  • the preferred anionic hybrid ultra-microporous material is [L 2 -Ni-A] n , in which the metal ion is Ni 2+ , which can realize the thermodynamic separation of the ethylene/ethane mixture.
  • the inorganic fluorine-containing anion A is GeF6 2- .
  • the volume ratio of ethylene to ethane in the mixed gas of ethylene and ethane is 1-50:50-99.
  • the anionic hybrid ultra-microporous material can separate ethane with a purity greater than 99.99% and ethylene gas with a purity of 80-99% from the ethylene/ethane mixed gas (content ratio is 1-50:50-99).
  • the present invention is based on the method for the adsorption and separation of ethylene/ethane based on anionic hybrid ultra-microporous materials.
  • the contact modes of the separated adsorption material and ethylene and ethane are fixed bed adsorption, fluidized bed adsorption, moving bed adsorption, and simulated moving bed adsorption. Any kind of.
  • a fixed bed adsorption separation method which includes the following steps:
  • the ethylene/ethane mixture is passed into the fixed bed adsorption column at the set flow rate, and the ethylene component that is strongly adsorbed or diffused quickly in the material pore is adsorbed on the adsorbent material
  • ethane that does not adsorb has a low adsorption capacity or is difficult to diffuse in the pores penetrates first to obtain high-purity ethane gas
  • the desorption includes desorption under reduced pressure, desorption at elevated temperature, desorption by inert gas purging, or using the product gas purging obtained from separation to decompose the strongly adsorbed ethylene group. Suck it out to obtain high-purity ethylene gas.
  • the adsorption temperature is -20 to 60°C, preferably 0 to 45°C.
  • the adsorption pressure is 1-10 bar.
  • the desorption temperature is 80-180°C, preferably 90-140°C, desorption under reduced pressure can be used, and the desorption pressure is 0 to 1 bar.
  • the purity of the separated ethane is greater than 99.99%, and the purity of the ethylene is 70-99.0%.
  • the method of the present invention is suitable for the separation of mixed gas of ethylene/ethane with different contents.
  • concentration of ethylene and ethane in the mixed gas can be between 1-99%.
  • the material has good stability and can withstand many gases.
  • the anionic hybrid ultra-microporous material used in the present invention has outstanding advantages such as easy availability of raw materials, low cost, simple preparation method and high hydrothermal stability, and has very good industrial application prospects;
  • the pore size of the anionic hybrid ultra-microporous material prepared by the present invention can be precisely adjusted to realize the selective recognition of ethylene, and at the same time, the selective separation of ethylene and ethane can be achieved through the dynamic diffusion rate, and high-purity ethylene can be obtained. , Ethane (99.99%);
  • the anionic hybrid ultra-microporous material used in the present invention has the advantage of adjustable force with adsorbate molecules. Its special one-dimensional pore structure and anion sites in the pores can achieve strong resistance to ethylene. It has the advantages of high adsorption capacity and high selectivity because of its weak force on ethane or exclusion outside the pores.
  • the separation method provided by the present invention has outstanding advantages such as low energy consumption and small equipment investment.
  • the adsorbent of the present invention is easy to regenerate, has high thermal stability, can be reused, and has a long service life.
  • the method has low energy consumption and low cost, and has significant industrial application prospects.
  • Figure 1 is the adsorption isotherm of CO 2 at 298K for the anionic hybrid ultra-microporous material GeFSIX-3-Ni obtained in Example 1.
  • Example 2 is a diagram of the crystal structure of the anionic hybrid ultramicroporous material GeFSIX-3-Ni obtained in Example 1.
  • Example 3 is the adsorption isotherm of ethylene and ethane at 298K for the anionic hybrid ultramicroporous material GeFSIX-3-Ni obtained in Example 1.
  • Figure 4 is the penetration curve of the anionic hybrid ultra-microporous material GeFSIX-3-Ni obtained in Example 2 at 298K to an ethylene/ethane (50/50) mixture.
  • 5 is the adsorption isotherm of ethylene and ethane at 298K for the anionic hybrid ultra-microporous material TIFSIX-3-Co obtained in Example 3.
  • Example 7 is the adsorption isotherm of ethylene and ethane at 298K for the anionic hybrid ultra-microporous material GeFSIX-3-Co obtained in Example 6.
  • Example 8 is the adsorption isotherm of ethylene and ethane at 298K for the anionic hybrid ultra-microporous material GeFSIX-3-Fe obtained in Example 8.
  • Fig. 9 is a kinetic adsorption curve of ethylene and ethane of the anionic hybrid ultra-microporous material GeFSIX-3-Fe obtained in Example 8 at 298K.
  • 10 is the adsorption isotherm of ethylene and ethane at 298K for the anionic hybrid ultra-microporous material TIFSIX-3-Ni obtained in Example 9.
  • Figure 11 is a diagram of the pore structure and material coordination structure of the ultramicroporous anion pillared hybrid material (Figure Represents a metal atom; Expressed as an inorganic fluoride anion, Represents organic ligands).
  • Figure 1 shows the CO 2 adsorption isotherm of GeFSIX-3-Ni material at 298K and 1atm;
  • Figure 2 is the structure diagram of the crystal unit of GeFSIX-3-Ni material, where Is an inorganic anion GeF 6 2- , Is the metal ion Ni 2+ ,
  • Is an inorganic anion GeF 6 2- Is the metal ion Ni 2+
  • For the organic ligand pyrazine In a single crystal unit, four organic ligands are connected to form a square frame through four metal end points, and four inorganic anions are connected to the metal ion end points through coordination bonds to form a crystal unit, and the crystal unit is connected along the axis through anion They are arranged in sequence to form a one-dimensional pipe-type pore structure, and the one-dimensional pipe-type pore structure is arranged regularly along the radial direction to form a GeFSIX-3-Ni material with a porous structure.
  • Table 1 shows the crystal structure parameters of GeFSIX-3-Ni material.
  • Figure 3 shows the static adsorption isotherm of GeFSIX-3-Ni on ethylene and ethane. It can be seen that GeFSIX-3-Ni preferentially adsorbs ethylene and has a higher capacity. In the pressure range of 0-1bar, the adsorption capacity of ethylene Both are higher than the adsorption capacity of ethane, indicating that GeFSIX-3-Ni preferentially adsorbs ethylene thermodynamically under normal pressure.
  • TIFSIX-3-Co material into a 15cm adsorption column, and pass a 0.2Mpa mixture of ethylene:ethane:methane (49:49:2) at 30°C into the adsorption column at 2mL/min. When it penetrates, stop the adsorption.
  • the adsorption column is vacuum desorbed at 130°C to obtain ethylene (purity greater than 90%), and the adsorption column can be recycled.
  • thermogravimetric curve of TIFSIX-3-Co material is shown in Figure 6.
  • the obtained GeFSIX-3-Co material was loaded into a 10cm adsorption column, and the 0.3Mpa ethylene:ethane (50:50) mixed gas was passed into the adsorption column at 0.5mL/min at 10°C to obtain high purity ethane gas (greater than 99.9%), when ethylene penetrates, stop the adsorption.
  • the adsorption column is vacuum desorbed at 100°C to obtain ethylene (purity greater than 98%), and the adsorption column can be recycled.
  • the static adsorption isotherm of GeFSIX-3-Fe on ethylene and ethane in Fig. 8 shows that the adsorption capacity of GeFSIX-3-Fe on ethylene is much higher than that of ethane, indicating that GeFSIX-3-Fe is thermodynamically Ethylene is preferentially adsorbed, and the force on ethylene is obviously stronger than that of ethane;
  • the kinetic adsorption curve of GeFSIX-3-Fe on ethylene and ethane in Fig. 9 shows that ethylene can quickly diffuse into the GeFSIX-3-Fe pores and reach a higher level. High adsorption capacity, while the ethane adsorption capacity changes slowly with time and the adsorption capacity is significantly lower than ethylene, indicating that GeFSIX-3-Fe preferentially adsorbs ethylene kinetics.
  • TIFSIX-3-Ni Load the obtained TIFSIX-3-Ni into a 10cm long adsorption column, and pass a 0.5Mpa ethylene:ethane (93:7) mixed gas into the adsorption column at 25°C at a rate of 0.5mL/min.
  • High-purity ethylene can be obtained from the effluent gas (Greater than 99.99%) gas, when ethylene penetrates, stop adsorption.
  • the adsorption column adopts 100°C vacuum desorption for 12h, and the adsorption column can be recycled.
  • NbFSIX- 3-Ni material Place 1mmol NiF 2 , 1mmol NH 4 NbF 6 and 12mmol pyrazine in the culture flask, add 1ml water and 2ml methanol, stir at room temperature for 48h, the slurry obtained is filtered by suction and vacuum activated at 100°C for 8h to obtain NbFSIX- 3-Ni material.

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Abstract

本发明公开了一种乙烯乙烷的分离方法，包括如下步骤：将乙烯与乙烷的混合气体与超微孔阴离子柱撑杂化材料接触，对乙烯分子进行选择性吸附，将乙烯与乙烷分离；超微孔阴离子柱撑杂化材料的表达通式为[L 2-M-A] n，由有机配体L、无机含氟阴离子A和金属离子M通过配位键构建而成，其中n为正整数，表示超微孔阴离子柱撑杂化材料由若干组成为L 2-M-A的结构单元规则排布而成；有机配体L为吡嗪；无机含氟阴离子A为SiF 6 2-、GeF 6 2-、TiF 6 2-、SnF 6 2-、NbF 6 -中的任意一种；金属离子M为Fe 2+、Co 2+、Ni 2+中的任意一种。本发明实现对乙烯的选择性识别，同时还可通过动力学扩散速率实现乙烯乙烷的选择性分离，可得到高纯度乙烯、乙烷(99.99％)。

Description

一种乙烯乙烷的分离方法 技术领域
本发明属于化工分离技术领域，具体涉及一种阴离子杂化超微孔材料用于乙烯乙烷的分离。
背景技术
乙烯作为重要的化工基础原料，主要来源于天然气及石油烃裂解，是世界上产量最大的化学产品之一，乙烯工业是石油化工产业的核心，乙烯产品占石化产品的75％以上，乙烯产量已作为衡量一个国家石油化工发展水平的重要标志之一，具有举足轻重的地位。乙烯主要用于生产聚乙烯、乙丙橡胶等聚合物，利用过程中需要达到高纯度。此外，乙烷可作为蒸汽裂解生产乙烯的主要原料，具有较高的需求量。
目前，工业乙烯乙烷分离主要工艺有深冷分离、吸收分离和吸附分离法，其中深冷分离法主要利用低温精馏，往往需要在较高压力和极低温度(-160℃)下通过原料中各组分挥发度差异实现分离，而乙烯/乙烷相对挥发度小，精馏塔塔板数通常大于100，使得该工艺能耗高、投资大、工艺复杂。因此开发高效、节能环保的乙烯乙烷分离方法迫在眉睫。
吸附分离法主要利用多孔吸附剂在常温常压下实现乙烯/乙烷分离，具有低能耗、低成本、操作工艺简单的优势，具有良好的工业应用前景。其核心为选择一种良好的吸附剂，理想的吸附剂应具有吸附容量大、分离因数大和使用寿命长等特点，而目前所利用的分子筛或多孔材料吸附剂存在吸附容量低或者选择性低的缺点，如NaY分子筛对常温常压下对乙烯的容量为2.1mmol/g，但乙烯/乙烷分离选择性仅为1.4(AICHE Journal,1995,41(3):509-517)；金属有机框架材料Cu(BTC) 2虽然在常温常压下对乙烯的吸附容量为6mmol/g，但乙烯/乙烷分离选择性仅为1.2(Micropor.Mesopor.Mater.,2002,55(2):217-230)；全硅分子筛ITQ-55通过乙烯、乙烷扩散的动力学差异实现乙烯/乙烷分离，但是常温常压下对乙烯吸附容量仅1.3mmol/g；专利CN 105251442A报道一种负载型CuCl吸附剂，乙烯 乙烷分离比可达8.25，但对乙烯吸附容量仅为1.25mmol/g，且该类材料容易失活，不利于工业应用。因此，亟需发展新的分离材料和分离方法。
发明内容
本发明提供一种乙烯乙烷的分离方法，实现对乙烯的选择性识别，同时还可通过动力学扩散速率实现乙烯乙烷的选择性分离，可得到高纯度乙烯、乙烷(99.99％)。
一种乙烯乙烷的分离方法，包括如下步骤：将乙烯与乙烷的混合气体与超微孔阴离子柱撑杂化材料接触，对乙烯分子进行选择性吸附，将乙烯与乙烷分离；
所述超微孔阴离子柱撑杂化材料的表达通式为[L 2-M-A] n，由有机配体L、无机含氟阴离子A和金属离子M通过配位键构建而成，其中n为正整数，表示所述超微孔阴离子柱撑杂化材料由若干组成为L 2-M-A的结构单元规则排布而成；
所述有机配体L为吡嗪；
所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、TiF 6 2-、SnF 6 2-、NbF 6 -中的任意一种；
所述金属离子M为Fe 2+、Co 2+、Ni 2+中的任意一种。
超微孔阴离子柱撑杂化材料的制备方法为将原料简单混合，然后1)以甲醇和水为溶剂，搅拌反应，然后真空干燥即得或者2)通过球磨机高速碰撞研磨后，甲醇洗涤干燥即得。
本发明中由上述有机配体L、无机含氟阴离子A和金属离子M通过配位键构建而成的超微孔阴离子柱撑杂化材料具有一维管道式孔道结构，孔径为
Figure PCTCN2020073769-appb-000001
材料的孔径为孔道中斜对角两个F原子之间的距离。所述超微孔阴离子柱撑杂化材料的孔道结构和材料配位结构如图11所示，由若干个结构单元规则排布而成：
图中
Figure PCTCN2020073769-appb-000002
表示金属原子；
Figure PCTCN2020073769-appb-000003
表示为无机含氟阴离子，
Figure PCTCN2020073769-appb-000004
表示有机配体。单个结构单元中三者排布方式为：四个有机配体通过四个金属 端点连接成一种正方形框架，无机阴离子通过配位键连接金属离子端点，进而无机阴离子连接另一结构单元行成三维框架结构。结构单元沿轴向依次排布形成一维管道式孔道结构(即图11中的其中一个孔道)，一维管道式孔道沿径向再规则排布形成多孔道杂化材料(图11为四个一维管道式孔道的排布图)。
本发明所采用的阴离子杂化超微孔材料由吡嗪有机配体、金属离子和无机含氟阴离子通过配位键构建得到，通过调节金属离子种类、无机含氟阴离子种类，实现孔径尺寸在
Figure PCTCN2020073769-appb-000005
之间精确调节，该材料具有一维孔道，每个孔道单元中含有4个阴离子，通过孔径限制、阴离子选择性识别作用及通过动力学扩散差异，可实现乙烯/乙烷的选择性吸附分离。
优选的，阴离子杂化超微孔材料为[L 2-Fe-A] n，其中金属离子为Fe 2+；可实现乙烯/乙烷混合气的热力学分离，也可实现乙烯/乙烷混合气的动力学分离；
优选的阴离子杂化超微孔材料为[L 2-Ni-A] n，其中金属离子为Ni 2+，可实现乙烯/乙烷混合气的热力学分离。
进一步地，所述金属离子M为Fe 2+时，所述无机含氟阴离子A为GeF6 2-。
优选地，所述乙烯和乙烷的混合气体中乙烯与乙烷的体积比为1-50：50-99。阴离子杂化超微孔材料可从乙烯/乙烷混合气(含量比为1-50：50-99)中分离出纯度大于99.99％的乙烷及80-99％的乙烯气体。
本发明基于阴离子杂化超微孔材料实现乙烯/乙烷吸附分离的方法，分离吸附材料与乙烯、乙烷的接触方式为固定床吸附、流化床吸附、移动床吸附、模拟移动床吸附中的任意一种。
优选地，采用固定床吸附分离法，包括如下步骤：
(1)在设定吸附温度、吸附压力下，按设定流速将乙烯/乙烷混合气通入固定床吸附柱中，强吸附或在材料孔内扩散快的乙烯组分吸附在吸附剂材料上，不吸附、吸附量低或难以在孔内扩散的乙烷先穿透，获得高纯度的乙烷气体；
(2)乙烯穿透后，进行脱附操作，脱附包括减压脱附、升温脱附、惰性气体吹扫脱附、或利用分离所得产品气体吹扫等方式，将强吸附的乙烯组分解吸出来，获得高纯度的乙烯气体。
吸附温度为-20～60℃，优选为0～45℃。
吸附压力为1～10bar。
脱附温度为80～180℃，优选为90～140℃，可采用减压脱附，脱附压力为0～1bar。
采用本发明所述方法，分离所得乙烷纯度大于99.99％、乙烯纯度为70-99.0％。
本发明所述方法适用于不同含量乙烯/乙烷混合气的分离，乙烯、乙烷在混合气中的浓度可在1-99％之间，该材料稳定性好，耐受很多气体。
与现有技术相比，具有如下有益效果：
(1)本发明所采用阴离子杂化超微孔材料具有原料易得、成本低、制备方法简单和水热稳定性高等突出优点，具有非常好的工业应用前景；
(2)本发明所制备的阴离子杂化超微孔材料孔径可精准调控，实现对乙烯的选择性识别，同时还可通过动力学扩散速率实现乙烯乙烷的选择性分离，可得到高纯度乙烯、乙烷(99.99％)；
(3)本发明采用的阴离子杂化超微孔材料相比传统吸附剂具有与吸附质分子作用力可调的优点，其特殊的一维孔道结构及孔道中阴离子作用位点可实现对乙烯强作用吸附，对乙烷作用力弱或者排阻于孔外，具有吸附容量高、选择性高的优势；
(4)本发明提供分离方法与传统溶剂吸收、萃取精馏和精密精馏技术相比，具有能耗低，设备投资小等突出优点。
(5)本发明吸附剂易再生，热稳定性高，可重复利用，使用寿命长，本方法低能耗、低成本，具有显著的工业应用前景。
附图说明
图1为实施例1所得阴离子杂化超微孔材料GeFSIX-3-Ni在298K下对CO 2的吸附等温线。
图2为实施例1所得阴离子杂化超微孔材料GeFSIX-3-Ni的晶体结构图。
图3为实施例1所得阴离子杂化超微孔材料GeFSIX-3-Ni在298K下对乙烯、乙烷的吸附等温线。
图4为实施例2所得阴离子杂化超微孔材料GeFSIX-3-Ni在298K下 对乙烯/乙烷(50/50)混合气的穿透曲线。图5为实施例3所得阴离子杂化超微孔材料TIFSIX-3-Co在298K下对乙烯、乙烷的吸附等温线。
图6为实施例3所得阴离子杂化超微孔材料TIFSIX-3-Co的热重曲线。
图7为实施例6所得阴离子杂化超微孔材料GeFSIX-3-Co在298K下对乙烯、乙烷的吸附等温线。
图8为实施例8所得阴离子杂化超微孔材料GeFSIX-3-Fe在298K下对乙烯、乙烷的吸附等温线。
图9为实施例8所得阴离子杂化超微孔材料GeFSIX-3-Fe在298K下对乙烯、乙烷的动力学吸附曲线。图10为实施例9所得阴离子杂化超微孔材料TIFSIX-3-Ni在298K下对乙烯、乙烷的吸附等温线。
图11为超微孔阴离子柱撑杂化材料的孔道结构和材料配位结构图(图中
Figure PCTCN2020073769-appb-000006
表示金属原子；
Figure PCTCN2020073769-appb-000007
表示为无机含氟阴离子，
Figure PCTCN2020073769-appb-000008
表示有机配体)。
具体实施方式
实施例1
将1mmol Ni(BF 4) 2、1mmol(NH 4) 2GeF 6和10mmol吡嗪置于菌种瓶中，加入3ml水和1ml甲醇，室温搅拌48h，所得料浆抽滤后在140℃抽真空条件下活化12h，得到GeFSIX-3-Ni材料。
将所得GeFSIX-3-Ni材料填装入5cm吸附柱中，25℃下将0.2Mpa的乙烯：乙烷(93.7：6.3)混合气以1mL/min通入吸附柱，流出气体中可获得高纯度乙烷(大于99.99％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(纯度大于98％)，吸附柱可循环使用。
图1为GeFSIX-3-Ni材料298K和1atm下对CO 2的吸附等温线；
图2为GeFSIX-3-Ni材料的晶体单元结构图，其中
Figure PCTCN2020073769-appb-000009
为无机阴离子 GeF 6 2-，
Figure PCTCN2020073769-appb-000010
为金属离子Ni 2+，
Figure PCTCN2020073769-appb-000011
为有机配体吡嗪。，单个晶体单元中，四个有机配体通过四个金属端点连接成一种正方形框架，四个无机阴离子通过配位键连接金属离子端点后行成一个晶体单元，晶体单元通过阴离子连接沿着轴向依次排布形成一维管道式孔道结构，一维管道式孔道结构沿径向规则排列形成多孔道结构的GeFSIX-3-Ni材料。
GeFSIX-3-Ni材料298K下对乙烯、乙烷的吸附等温线如图3所示；
表1为GeFSIX-3-Ni材料的晶体结构参数。
表1
Figure PCTCN2020073769-appb-000012
图3所示GeFSIX-3-Ni对乙烯和乙烷的静态吸附等温线可以看出，GeFSIX-3-Ni优先吸附乙烯，并具有较高容量，在0-1bar气压范围内，乙烯的吸附量均高于乙烷吸附量，表明GeFSIX-3-Ni在常压下热力学上优先吸附乙烯。
实施例2
将1mmol Ni(NO 3) 2、1mmol(NH 4) 2GeF 6和3mmol吡嗪置于球磨罐 中，以800r/min球磨15min后，将所得物质10ml甲醇洗涤后抽滤，100℃抽真空活化12h，得到GeFSIX-3-Ni材料。
将所得GeFSIX-3-Ni材料填装入10cm吸附柱中，25℃下将0.5Mpa的乙烯：乙烷(50：50)混合气以0.5mL/min通入吸附柱，流出气体中可获得高纯度乙烷(大于99.99％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(纯度大于95％)，吸附柱可循环使用。
GeFSIX-3-Ni材料298K及1atm下对乙烯/乙烷(50/50)混合气的穿透曲线如图4所示。
实施例3
将1mmol Co(NO 3) 2、1mmol(NH 4) 2TiF 6和12.5mmol吡嗪置于菌种瓶中，加入2ml甲醇和1ml水后，室温搅拌48h，所得料浆抽滤后，140℃抽真空活化24h，得到TIFSIX-3-Co材料。
将所得TIFSIX-3-Co材料填装入15cm吸附柱中，30℃下将0.2Mpa的乙烯：乙烷：甲烷(49：49：2)混合气以2mL/min通入吸附柱，当乙烯穿透时，停止吸附。吸附柱采用130℃抽真空解吸附，得到乙烯(纯度大于90％)，吸附柱可循环使用。
TIFSIX-3-Co材料298K时对乙烯、乙烷的吸附等温线如图5所示；
TIFSIX-3-Co材料的热重曲线如图6所示。
实施例4
将1mmol Ni(NO 3) 2、1mmol(NH 4) 2SnF 6和12mmol吡嗪置于菌种瓶中，加入2ml甲醇和2ml水后，室温搅拌48h，所得料浆抽滤后，150℃抽真空活化24h，得到SNFSIX-3-Ni材料。
将所得SNFSIX-3-Ni材料填装入10cm吸附柱中，20℃下将0.2Mpa的乙烯：乙烷：乙炔(49：49：2)混合气以1mL/min通入吸附柱，流出气体中可获得高纯度乙烷(大于99.99％)气体，当乙烯穿透时，停止吸附。吸附柱采用120℃抽真空解吸附，吸附柱可循环使用。
实施例5
将2mmol Co(NO 3) 2、1mmol(NH 4) 2SnF 6和4mmol吡嗪置于菌种瓶中，加入20ml甲醇和20ml水后，溶剂热120℃处理72h，所得产品过滤，140℃抽真空活化24h，得到SNFSIX-3-Co材料。
将所得SNFSIX-3-Co材料填装入5cm吸附柱中，30℃下将0.2Mpa的乙烯：乙烷：二氧化碳(49：49：2)混合气以2mL/min通入吸附柱，流出气体中可获得高纯度乙烷(大于99.99％)气体，当乙烯穿透时，停止吸附。吸附柱采用130℃抽真空解吸附，吸附柱可循环使用。
实施例6
将1mmol Co(BF 4) 2、1mmol(NH 4) 2GeF 6和13mmol吡嗪置于菌种瓶中，加入2ml甲醇和1ml水后，室温搅拌48h，所得料浆抽滤后，140℃抽真空活化24h，得到GeFSIX-3-Co材料。
将所得GeFSIX-3-Co材料装入10cm吸附柱，10℃下将0.3Mpa的乙烯：乙烷(50：50)混合气以0.5mL/min通入吸附柱，得到高纯度乙烷气体(大于99.9％)，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(纯度大于98％)，吸附柱可循环使用。
GeFSIX-3-Co材料298K时对乙烯、乙烷的吸附等温线如图7所示。
实施例7
将1mmol Fe(BF 4) 2、1mmol(NH 4) 2GeF 6和12.5mmol吡嗪置于菌种瓶中，加入2ml水和1ml甲醇后，室温搅拌48h，所得料浆抽滤后，140℃抽真空活化24h，得到GeFSIX-3-Fe材料。
实施例8
采用溶剂热方法，将2mmol Fe(NO 3) 2、1mmol(NH 4) 2GeF 6和5mmol吡嗪溶于20ml甲醇和水(体积比1：1)的混合溶液中，80℃反应72h后甲醇洗涤、抽滤，所得产品140℃下抽真空活化12h，得到GeFSIX-3-Fe材料。
GeFSIX-3-Fe材料298K时对乙烯、乙烷的吸附等温线如图8所示；
GeFSIX-3-Fe材料298K时对乙烯、乙烷的动力学吸附曲线如图9所示。
图8中GeFSIX-3-Fe对乙烯和乙烷的静态吸附等温线可以看出，GeFSIX-3-Fe对乙烯的吸附量远远高于乙烷的吸附量，表明热力学上GeFSIX-3-Fe优先吸附乙烯，并且对乙烯的作用力明显强于乙烷；图9中GeFSIX-3-Fe对乙烯和乙烷的动力学吸附曲线表明乙烯可以快速扩散至GeFSIX-3-Fe孔道内并达到较高吸附量，而乙烷吸附量随时间变化缓慢并且吸附量明显低于乙烯，表明GeFSIX-3-Fe动力学上优先吸附乙烯。
实施例9
将1mmol Ni(BF 4) 2、1mmol(NH 4) 2TiF 6和14mmol吡嗪置于菌种瓶中，加入2ml水和1ml甲醇后，室温搅拌48h，所得料浆抽滤后，150℃抽真空活化8h，得到TIFSIX-3-Ni材料。
将所得TIFSIX-3-Ni装入10cm长吸附柱，25℃下将0.5Mpa的乙烯：乙烷(93：7)混合气以0.5mL/min通入吸附柱，流出气体中可获得高纯度乙烯(大于99.99％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附12h，吸附柱可循环使用。
0℃下将乙烯、乙烷(50：50)混合气以1mL/min通入实施例15吸附柱，流出气体中可获得高纯度乙烷(大于99.9％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(大于97％)，吸附柱可循环使用。
TIFSIX-3-Ni材料298K时对乙烯、乙烷的吸附等温线如图10所示。
实施例10
将1mmol NiF 2、1mmol NH 4NbF 6和12mmol吡嗪置于菌种瓶中，加入1ml水和2ml甲醇后，室温搅拌48h，所得料浆抽滤后，100℃抽真空活化8h，得到NbFSIX-3-Ni材料。
将所得NbFSIX-3-Ni装入15cm长吸附柱，25℃下将0.1Mpa的乙烯：乙烷(50：50)混合气以0.5mL/min通入吸附柱，流出气体中可获得高纯度乙烯(大于99.9％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(纯度大于85％)，吸附柱可循环使用。
实施例11
将1mmol Ni(BF 4) 2、1mmol(NH 4) 2SiF 6和2.5mmol吡嗪置于球磨罐中，以600r/min转速球磨30min，所得物质用20mL甲醇洗涤，120℃抽真空活化24h，得到SIFSIX-3-Ni材料。
将所得SIFSIX-3-Ni装入5cm长吸附柱，15℃下将0.2Mpa的乙烯：乙烷(50：50)混合气以0.5mL/min通入吸附柱，流出气体中可获得高纯度乙烯(大于99.9％)气体，当乙烯穿透时，停止吸附。吸附柱采用100℃抽真空解吸附，得到乙烯(纯度大于90％)，吸附柱可循环使用。
以上所述仅为本发明专利的具体实施案例，但本发明专利的技术特征并不局限于此，任何相关领域的技术人员在本发明的领域内，所作的变化或修饰皆涵盖在本发明的专利范围之中。

Claims (8)

  1. 一种乙烯乙烷的分离方法，其特征在于，包括如下步骤：将乙烯与乙烷的混合气体与超微孔阴离子柱撑杂化材料接触，超微孔阴离子柱撑杂化材料对乙烯分子进行选择性吸附，将乙烯与乙烷分离；
    所述超微孔阴离子柱撑杂化材料的表达通式为[L 2-M-A] n，由有机配体L、无机含氟阴离子A和金属离子M通过配位键构建而成，其中n为正整数，表示所述超微孔阴离子柱撑杂化材料由若干组成为L 2-M-A的结构单元规则排布而成；
    所述有机配体L为吡嗪；
    所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、TiF 6 2-、SnF 6 2-、NbF 6 -中的任意一种；
    所述金属离子M为Fe 2+、Co 2+、Ni 2+中的任意一种。
  2. 根据权利要求1所述乙烯乙烷的分离方法，其特征在于，所述超微孔阴离子柱撑杂化材料具有一维管道式孔道结构，孔径为
    Figure PCTCN2020073769-appb-100001
  3. 根据权利要求1所述乙烯乙烷的分离方法，其特征在于，所述金属离子M为Fe 2+或Ni 2+。
  4. 根据权利要求1所述乙烯乙烷的分离方法，其特征在于，所述乙烯和乙烷的混合气体中乙烯与乙烷的体积比为1-50：50-99。
  5. 根据权利要求1所述乙烯乙烷的分离方法，其特征在于，混合气体与超微孔阴离子柱撑杂化材料的接触方式为固定床吸附、流化床吸附、移动床吸附中的任意一种。
  6. 根据权利要求1所述乙烯乙烷的分离方法，其特征在于，混合气体与超微孔阴离子柱撑杂化材料的接触方式为固定床吸附，包括如下步骤：
    (1)在设定吸附温度、吸附压力下，按设定流速将乙烯/乙烷混合气通入固定床吸附柱中，乙烯组分吸附在吸附剂材料上，乙烷先穿透，获得乙烷气体；
    (2)乙烯穿透后，进行脱附操作，从吸附剂材料中解析乙烯组分，得到乙烯气体。
  7. 根据权利要求6所述乙烯乙烷的分离方法，其特征在于，步骤(1) 中吸附温度为-20～60℃；吸附压力为1～10bar。
  8. 根据权利要求6所述乙烯乙烷的分离方法，其特征在于，步骤(2)中脱附温度为80～180℃；脱附压力为0～1bar。
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