WO2020156423A1 - Procédé permettant de séparer l'éthylène de l'éthane - Google Patents

Procédé permettant de séparer l'éthylène de l'éthane Download PDF

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Publication number
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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PCT/CN2020/073769
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English (en)
Chinese (zh)
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邢华斌
张照强
崔希利
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浙江大学
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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

Definitions

  • 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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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'invention concerne un procédé permettant de séparer l'éthylène de l'éthane, comprenant les étapes suivantes consistant à : mettre en contact un mélange d'éthylène et d'éthane avec un matériau hybride ultramicroporeux à pontage d'anions, et adsorber de manière sélective les molécules d'éthylène de façon à séparer l'éthylène de l'éthane, le matériau hybride ultramicroporeux à pontage d'anions étant exprimé par la formule générale [L2-M-A]n, celui-ci étant construit par un ligand organique L, un anion A inorganique contenant du fluor et un ion métallique M par l'intermédiaire de liaisons de coordination, n étant un nombre entier positif, qui représente le fait que le matériau hybride ultramicroporeux à pontage d'anions est formé par agencement régulier de plusieurs unités structurales composées de L2-M-A ; le ligand organique L est de la pyrazine ; l'anion A inorganique contenant du fluor est l'un quelconque de SiF6 2-, GeF6 2-, TiF6 2-, SnF6 2- et NbF6 - ; et l'ion métallique M est l'un quelconque parmi Fe2+, Co2+ et Ni2+. L'invention réalise une identification sélective de l'éthylène et, en même temps, une séparation sélective de l'éthylène et de l'éthane au moyen d'un taux de diffusion cinétique, ce qui permet d'obtenir une pureté élevée (99,99 %) d'éthylène et d'éthane.
PCT/CN2020/073769 2019-01-29 2020-01-22 Procédé permettant de séparer l'éthylène de l'éthane WO2020156423A1 (fr)

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CN109651055B (zh) * 2019-01-29 2020-06-05 浙江大学 一种乙烯乙烷的分离方法
EP3791949A1 (fr) * 2019-09-13 2021-03-17 University of Limerick Améliorations relatives à la séparation des gaz
CN114870806B (zh) * 2022-04-19 2023-04-18 浙江大学 一种离子杂化多孔材料在分离环己烯和环己烷中的应用及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015195791A1 (fr) * 2014-06-17 2015-12-23 King Abdullah University Of Science And Technology Procédés écologiques de préparation de structures organiques métalliques hautement sélectives au co2 et tolérantes au h2s
CN105949028A (zh) * 2016-06-20 2016-09-21 太原理工大学 材料tut-o2作为吸附剂在分离乙烯中低浓度乙烷中的应用
WO2017132816A1 (fr) * 2016-02-02 2017-08-10 University Of Limerick Procédés de séparation de gaz
CN109651055A (zh) * 2019-01-29 2019-04-19 浙江大学 一种乙烯乙烷的分离方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530717B2 (en) * 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene
CN103193578A (zh) * 2013-04-08 2013-07-10 浙江师范大学 一种利用金属有机骨架材料分离丙烯和丙烷的方法
CN105713017A (zh) * 2014-12-05 2016-06-29 中国石油化工股份有限公司 一种高选择性金属有机骨架材料及其制备方法
US10335779B2 (en) * 2015-04-07 2019-07-02 King Abdullah University Of Science And Technology Highly stable Ni-M F6-NH2O/onpyrazine2(solvent)X metal organic frameworks and methods of use
CN105944680B (zh) * 2016-05-17 2018-12-25 浙江大学 一种吸附分离丙烯丙炔的方法
CN108014752B (zh) * 2016-11-03 2019-09-20 浙江大学 一种用于分离乙烷和乙烯的金属有机框架材料及乙烯乙烷的分离方法
GB2562309A (en) * 2017-05-12 2018-11-14 Univ Belfast Porous liquids
CN108671893B (zh) * 2018-04-24 2021-03-30 浙江大学 一种用于分离乙烯和乙炔的金属有机框架材料及乙烯乙炔的分离方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015195791A1 (fr) * 2014-06-17 2015-12-23 King Abdullah University Of Science And Technology Procédés écologiques de préparation de structures organiques métalliques hautement sélectives au co2 et tolérantes au h2s
US20170137450A1 (en) * 2014-06-17 2017-05-18 King Abdullah University Of Science And Technology Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks
WO2017132816A1 (fr) * 2016-02-02 2017-08-10 University Of Limerick Procédés de séparation de gaz
CN105949028A (zh) * 2016-06-20 2016-09-21 太原理工大学 材料tut-o2作为吸附剂在分离乙烯中低浓度乙烷中的应用
CN109651055A (zh) * 2019-01-29 2019-04-19 浙江大学 一种乙烯乙烷的分离方法

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