WO2021169764A1 - Matériau poreux en couches pour adsorber et séparer l'allylène et le propylène, son procédé de préparation et son application - Google Patents

Matériau poreux en couches pour adsorber et séparer l'allylène et le propylène, son procédé de préparation et son application Download PDF

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WO2021169764A1
WO2021169764A1 PCT/CN2021/075163 CN2021075163W WO2021169764A1 WO 2021169764 A1 WO2021169764 A1 WO 2021169764A1 CN 2021075163 W CN2021075163 W CN 2021075163W WO 2021169764 A1 WO2021169764 A1 WO 2021169764A1
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propyne
propylene
adsorption
porous material
layered porous
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Chinese (zh)
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杨启炜
柯天
任其龙
杨亦文
张治国
鲍宗必
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浙江大学
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Definitions

  • the invention relates to the technical field of chemical engineering, in particular to a layered porous material used for the adsorption and separation of propargylpropene, and a preparation method and application thereof.
  • Propylene is an important olefin product in the world's petrochemical industry. It is mainly derived from steam cracking in industry. It is mainly used for the production of polymerized monomers such as polypropylene and other downstream products. It is widely used in various national economic industries such as plastics, pharmaceuticals, textiles, and coatings. Propyne is a by-product obtained with the production of propylene. The separation of propyne and propylene is a crucial step in industrial production. Since the molecular size of propyne/propylene is similar and the physical properties are similar, the separation between propyne/propylene gas exists Considerable technical challenge.
  • cryogenic rectification has very high requirements on operating conditions and equipment.
  • the relatively high pressure and extremely low temperature required for this separation method have high energy consumption, and the process flow is complex, so the equipment investment is large.
  • Selective catalytic hydrogenation is the selective catalytic hydrogenation of propyne in propylene and propyne under the action of a catalyst to obtain propylene to achieve the purpose of olefin purification, but because the concentration ratio of propylene component in the mixed gas is usually higher than that of propyne component High, so that the reaction exists in the transitional hydrogenation of propylene to obtain low-value-added propane, and the energy consumption of the separation method is relatively high, so it is extremely important to develop a new type of high-efficiency and energy-saving separation method.
  • Adsorption separation technology is a low-energy gas separation technology. It has the advantages of low cost, simple process flow and high separation efficiency. It can realize the separation of low-carbon hydrocarbons under normal temperature and pressure conditions, and has good industrial application prospects.
  • metal-organic framework materials have made great progress in the separation of propylene and propyne due to their pore structure diversity and fine controllability.
  • Some existing metal-organic framework materials have been able to achieve high propyne adsorption capacity, but at the same time they also adsorb a certain amount of propylene, which requires repeated separation after desorption, which increases separation energy consumption and theoretical trays. number.
  • the ideal adsorbent material not only needs to have a certain amount of propyne adsorption, but also completely exclude propylene.
  • the current metal-organic framework materials are difficult to achieve adsorption of propyne while exclusion of propylene.
  • the patent specification with publication number CN 105944680 A discloses a method for the adsorption and separation of propylene and propyne, using an anion-containing metal-organic framework material adsorbent.
  • a large number of anionic active sites and their highly ordered spatial arrangement make it show excellent propyne adsorption performance.
  • the present invention provides a layered porous material for the adsorption and separation of propargyl propylene, which is prepared by cleverly combining specific metal ions, inorganic anions, and special organic ligands.
  • the degree of layer-to-layer stacking and the pore size within the layer can be precisely controlled by changing the metal site or the type of inorganic anion, which is the first time to achieve propylene exclusion.
  • the kinetic diameters of propyne and propylene are with The difference is smaller than the difference in the dynamic diameter of acetylene and ethylene, and both propyne molecules and propylene molecules contain methyl groups, and their structures are very similar, making the separation of propyne and propylene more difficult than the separation of acetylene and ethylene.
  • the pore size of the adsorbent can be controlled more precisely to achieve efficient separation.
  • a layered porous material for the adsorption and separation of propargyl propylene has periodic intralayer diamond-shaped pores and interlayer fold-line pores. It consists of metal ions M, inorganic anions A and organic ligands L through coordination bonds and supramolecular The function is formed, and the general structure is ML 2 A;
  • the metal ion M is at least one of Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+;
  • the inorganic anion A is TiF 6 2-, GeF 6 2-, NbOF 5 -, ZrF 6 2-, at least one of SnF 6 2-;
  • the structural formula of the organic ligand L is:
  • R 1 to R 8 are each independently selected from H, F, Cl, Br, I, CH 3 , NH 2 , OH, or COOH.
  • the metal ion M is simultaneously bridged with the organic ligand L and the inorganic anion A through coordination bonds to form a two-dimensional network, and adjacent two-dimensional networks are stacked by supramolecular action to form a layered porous structure.
  • this type of layered material can achieve the adsorption of propyne molecules and the exclusion of propylene molecules through the selective response mechanism of ligand conformation and interlayer stacking mode to different guest molecules, and through the distribution in the pores
  • the high-density anion sites have strong hydrogen bond interactions with propyne molecules, achieving high propyne capacity while achieving propylene exclusion.
  • the present invention finds that a layered porous material with the structural formula Cu(C 12 H 8 N 2 S) 2 GeF 6 (denoted as GeFSIX-dps-Cu) excludes propylene, and the adsorption capacity for propylene under normal temperature and pressure is only 0.08mmol/g, while the adsorption capacity for propyne is as high as 3.73mmol/g, and the IAST (Ideal Adsorbed Solution Theory) selectivity for propyne/propylene mixed gas with a volume ratio of 50:50 and 10:90 is as high as 10 7 , Much higher than other adsorbents.
  • This type of material can obtain higher propyne adsorption capacity under low pressure.
  • the present invention has found that the layered porous material with the structural formula Cu(C 12 H 8 N 2 S) 2 GeF 6 has a positive effect on propyne at 298K and 0.1bar. Its adsorption capacity is 3.15mmol/g, and its adsorption capacity for propylene is almost 0, achieving high propyne adsorption capacity while completely exclusion of propylene.
  • the metal ion M is at least one of Cu 2+ and Zn 2+;
  • the inorganic anion A is at least one of TiF 6 2- and GeF 6 2-;
  • R 1 , R 4 , R 5 , and R 8 are independently selected from any one of H, Cl, Br, I, OH, NH 2 , and CH 3 , R 2 , R 3 , R 6 and R 7 are each independently selected from any one of H, OH, and NH 2.
  • the organic ligand L is 4,4'-dipyridine sulfide (dps).
  • the obtained layered porous material can better realize the exclusion of propylene while ensuring a larger propyne adsorption capacity.
  • the layered porous material can be synthesized by any one of the solid-phase grinding method, the interface slow diffusion method, the solvothermal method, and the room temperature co-precipitation method commonly used in the art, and the following preparation method is preferably used:
  • the layered porous material is prepared by hydrothermal synthesis with the precursor of metal ion M, inorganic anion A and organic ligand L.
  • the organic ligand L and metal ion M in the initial reaction system
  • the molar ratio and the molar ratio of the organic ligand L to the inorganic anion A are both 2:1, and the reaction temperature is 25-85°C.
  • the layered porous material obtained by the preferred preparation method is more conducive to the adsorption and separation of propargylpropene.
  • the invention also provides the application of the layered porous material in the adsorption and separation of propargyl propylene.
  • the layered porous material is GeFSIX-dps-Zn, that is, the metal ion M is Zn 2+ , the inorganic anion A is GeF 6 2- , and the organic ligand L is 4,4-dipyridine sulfide.
  • Ether (dps) The materials under 1bar, 298K conditions propynyl, propene adsorption capacity were 3.48mmol g -1, 0.12mmol g -1.
  • the layered porous material is GeFSIX-dps-Cu, that is, the metal cation is Cu 2+ , the inorganic anion is GeF 6 2- , and the organic ligand is 4,4-dipyridine sulfide.
  • the adsorption capacity of the above two preferred materials for propylene is less than 0.1 propylene molecules/unit cell, and it can be considered that the complete exclusion of propylene is achieved.
  • the present invention also provides a method for adsorbing and separating propyne and propylene.
  • the layered porous material is used as an adsorbent, and the adsorbent is in contact with a mixed gas containing propyne and propylene to selectively adsorb propyne to achieve propylene and propylene. Separation of alkynes.
  • the adsorbent When the mixed gas containing propylene and propyne is in contact with the layered porous material, the adsorbent selectively adsorbs propyne molecules and excludes propylene molecules due to the difference in propylene/propyne molecular size and hydrogen bond acidity.
  • the volume ratio of propyne to propylene is 1:99 to 99:1.
  • the volume ratio of the propyne component and the propylene component in the mixed gas is 1:99 to 99:1 (such as 50:50, 10:90, etc.), and the mixed gas may also contain hydrogen, nitrogen, oxygen, and carbon oxides ( Impurity components such as carbon monoxide, carbon dioxide, etc.), moisture and other low-carbon hydrocarbons (such as methane, propane, etc.) do not affect the adsorption and separation performance of the layered porous material for propyne/propylene components.
  • propylene with a purity (relative to the purity of propyne) greater than 99.99% can be separated from a mixed gas containing propyne and propylene.
  • the adsorption temperature is -20 to 60° C., and the adsorption pressure is 0.5 to 10 bar.
  • Lowering the adsorption temperature is beneficial to increase the propyne adsorption capacity, and increasing the adsorption temperature is conducive to narrowing the temperature difference between the desorption process, reducing the energy consumption required for the separation process, and increasing the diffusion rate of propyne in the pores. Therefore, considering the above two factors comprehensively, it is more preferable that the adsorption temperature is 0 to 35°C.
  • the adsorption pressure is further preferably 1 to 5 bar.
  • the adsorbent selectively adsorbs propyne and then desorbs to obtain propyne-rich gas
  • the desorption temperature is preferably 25 to 120°C, more preferably 45 to 100°C;
  • the desorption pressure is preferably 0 to 0.1 bar.
  • the contact mode of the adsorbent and the mixed gas containing propyne and propylene can be at least one of fixed bed adsorption, fluidized bed adsorption, and moving bed adsorption.
  • the contact mode between the adsorbent and the mixed gas containing propyne and propylene is fixed bed adsorption, which specifically includes the steps: under a set adsorption temperature and pressure, the mixed gas containing propyne and propylene is passed through Into the fixed-bed adsorption column filled with the adsorbent, the propylene component preferentially penetrates the bed, and the propylene gas with a propyne content of less than 0.01 vol% is directly obtained from the outlet of the adsorption column, and the propyne component is enriched in the bed. Propyne-rich gas is obtained by desorption.
  • the propylene component has a weak interaction with the layered porous material, has a small amount of adsorption, and preferentially penetrates the fixed bed, and can directly obtain propylene gas containing very low content of propyne (less than 0.01 vol%).
  • the propyne component has a strong interaction with the layered porous material and is enriched in a fixed bed. After it penetrates (adsorption saturation), it is decompressed, heated, purged with inert gas, purged with product gas, or various desorptions. The combined method decomposes and absorbs the adsorbed propyne group to obtain high-purity (greater than 99.99%) propyne gas.
  • the main advantages of the present invention include:
  • the present invention provides a new method for the adsorption and separation of propyne and propylene by using a layered porous material.
  • the adsorption capacity of the material for propyne under equilibrium conditions is significantly higher than that of propylene, thereby realizing effective separation of propyne and propylene.
  • the layered porous material used in the present invention can achieve exclusion of propylene and has a higher propyne adsorption capacity, so that it can obtain high-purity propylene at the same time after desorption. High-purity propyne can be obtained.
  • the layered porous material used in the present invention has a simple synthesis method, has the advantages of large adsorption capacity, high selectivity, recyclability, etc., and has excellent stability.
  • the thermal decomposition temperature is close to 200 °C, and it is exposed to the air ( 25°C, relative humidity 70%) The crystal structure remains intact and the specific surface area does not decrease significantly after being immersed in water for 72 hours, which has a good industrial application prospect;
  • the separation method provided by the present invention can simultaneously obtain propylene gas with a purity of up to 99.99% and propyne gas with a purity of up to 99.99%;
  • the separation method provided by the present invention has outstanding advantages such as mild operating conditions, energy saving and environmental protection, and small equipment investment, and is expected to bring economic benefits to small and medium-sized enterprises.
  • Figure 1 is a thermogravimetric curve diagram of the layered porous material GeFSIX-dps-Cu obtained in Example 1;
  • Example 4 is a thermogravimetric curve diagram of the layered porous material GeFSIX-dps-Zn obtained in Example 2;
  • Figure 7 is a fixed bed penetration curve of the layered porous material GeFSIX-dps-Cu obtained in Example 1 to a propylene/propyne (50:50) mixed gas; where C 0 represents the component concentration of the raw material at the outlet of the adsorption column, C A represents the initial concentration of raw materials;
  • FIG. 8 is a fixed bed penetration curve diagram of the layered porous material GeFSIX-dps-Cu obtained in Example 1 to a propylene/propyne (10:90) mixed gas;
  • thermogravimetric curve of the GeFSIX-dps-Cu layered porous material obtained in this embodiment is shown in FIG. 1, and has high thermal stability.
  • the adsorption isotherm of the GeFSIX-dps-Cu layered porous material obtained in this example for propyne propylene at 298K is shown in Figure 2.
  • the material has a relatively high propyne adsorption capacity (3.73 mmol/g) at room temperature and pressure. ) And at the same time exclude propylene.
  • the adsorption isotherm of the GeFSIX-dps-Cu layered porous material obtained in this example for propyne propylene at 273K is shown in Figure 3.
  • the material has a high propyne adsorption capacity (3.87mmol/ g) and at the same time exclude propylene.
  • thermogravimetric curve of the GeFSIX-dps-Zn layered porous material obtained in this embodiment is shown in FIG. 4, which has high thermal stability.
  • the adsorption isotherm of the GeFSIX-dps-Zn layered porous material obtained in this example for propyne propylene at 273K is shown in Figure 6.
  • the material has a high propyne adsorption capacity (3.78mmol/ g) and at the same time exclude propylene.
  • the GeFSIX-dps-Cu obtained in Example 1 was loaded into a 10cm-long fixed-bed adsorption column, and a mixed gas of propyne/propylene (50:50 by volume) was passed into the adsorption column at a flow rate of 0.5mL/min at room temperature.
  • High-purity propylene (highest purity greater than 99.99%) is obtained from the effluent gas.
  • the adsorption is stopped, and high-purity propyne (greater than 99.99%) can be obtained by desorption with He gas purging at 80°C for 15 hours.
  • Adsorption column Can be recycled.
  • the penetration curve of this example is shown in Figure 7.
  • the propylene component penetrates at 7 min/g and the retention time of the propyne component reaches 156 min/g.
  • the material has a high dynamic propyne adsorption capacity and at the same time excludes propylene. .
  • the GeFSIX-dps-Cu obtained in Example 1 was loaded into a 10cm-long fixed-bed adsorption column, and the propyne/propylene (volume ratio 10:90) mixed gas was passed into the adsorption column at a flow rate of 2mL/min at room temperature, and then flowed out Obtain high-purity propylene from the gas (the highest purity is greater than 99.99%).
  • the adsorption column can be recycled. use.
  • the penetration curve of this example is shown in Figure 8.
  • the material When the propylene component penetrates at 3.6 min/g and the retention time of the propyne component reaches 36.5 min/g, the material has a relatively high dynamic propyne adsorption capacity and discharges at the same time. Propylene resistance.
  • the GeFSIX-dps-Zn obtained in Example 2 was loaded into a 5 cm long fixed-bed adsorption column, and the propyne/propylene (volume ratio 50:50) mixed gas was passed into the adsorption column at a flow rate of 0.5 mL/min at room temperature.
  • High-purity propylene (highest purity greater than 99.99%) is obtained from the effluent gas.
  • the adsorption is stopped, and high-purity propyne (greater than 99.99%) can be obtained by desorption with He gas purging at 80°C for 15 hours.
  • Adsorption column Can be recycled.
  • the GeFSIX-dps-Zn obtained in Example 2 was loaded into a 5cm-long fixed-bed adsorption column, and the propyne/propylene (volume ratio 10:90) mixed gas was passed into the adsorption column at a flow rate of 2mL/min at room temperature, and flowed out Obtain high-purity propylene from the gas (the highest purity is greater than 99.99%).
  • the adsorption column can be recycled. use.
  • the penetration curve of this embodiment is shown in FIG. 9, the propylene component penetrates at 0.1 min/g and the retention time of the propyne component reaches 10.7 min/g.
  • propyne penetrates, stop the adsorption and desorption by He gas purging at 100°C for 15h. High-purity propyne (greater than 99.99%), the adsorption column maintains its desorption performance and can be recycled.

Abstract

Un matériau poreux en couches destiné à adsorber et à séparer l'allylène et le propylène, lequel présente des canaux à pores rhombiques intra-couches périodiques et des canaux à pores de type à ligne brisée inter-couche, est formé par un ion métallique M, un anion inorganique A et un ligand organique L au moyen d'une liaison de coordination et d'une interaction supramoléculaire, et a une formule générale structurale de ML2A. L'ion métallique M est au moins un élément parmi Fe2+, Co2+, Ni2+, Cu 2+, et Zn 2+. L'anion inorganique A est au moins un élément parmi TiF6 2-, GeF6 2-, NbOF5 -, ZrF6 2-, et SnF 6 2-. La formule structurale du ligand organique L est la suivante : (I), où R1-R8 sont chacun indépendamment choisis parmi H, F, Cl, Br, I, CH3, NH2, OH, ou COOH. Le matériau poreux en couches est un adsorbant, et l'adsorbant est en contact avec un gaz mixte contenant de l'allylène et du propylène pour adsorber sélectivement l'allylène, ce qui permet de mettre en œuvre la séparation du propylène et de l'allylène.
PCT/CN2021/075163 2020-02-27 2021-02-04 Matériau poreux en couches pour adsorber et séparer l'allylène et le propylène, son procédé de préparation et son application WO2021169764A1 (fr)

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