WO2025124336A1 - 具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用 - Google Patents

具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用 Download PDF

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WO2025124336A1
WO2025124336A1 PCT/CN2024/137778 CN2024137778W WO2025124336A1 WO 2025124336 A1 WO2025124336 A1 WO 2025124336A1 CN 2024137778 W CN2024137778 W CN 2024137778W WO 2025124336 A1 WO2025124336 A1 WO 2025124336A1
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propylene
molecular sieve
adsorption
propane
point
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French (fr)
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邢华斌
崔稷宇
杨立峰
崔希利
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Zhejiang University
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Zhejiang University
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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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/08—Propane
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/60—Use in several different columns

Definitions

  • the invention relates to the technical field of molecular sieves and chemical separation, and in particular to a molecular sieve with a point screening structure, a preparation method thereof and application thereof in the adsorption separation of propylene and propane.
  • propylene is one of the chemicals with the largest output in the world. Its downstream products mainly include polypropylene, propylene oxide, acrylonitrile, etc., which are widely used in various national economic industries such as plastics, pharmaceuticals, textiles, and coatings.
  • the production of propylene in industry is mainly separated and prepared from the mixture of low-carbon hydrocarbons cracked from naphtha.
  • the key and technical difficulty of low-carbon hydrocarbon separation lies in the separation of ethylene/ethane and propylene/propane with similar molecular sizes and similar physical properties.
  • the separation technology of propylene and propane mainly includes cryogenic distillation, solvent absorption, membrane separation, and adsorption separation.
  • cryogenic distillation technology has the most mature development and is widely used in industry.
  • the solvent absorption method not only has the problem of large organic solvent pollution, but also has low selectivity; the membrane separation method is limited in industrial application due to the low selectivity of existing membranes, complex membrane manufacturing process and high cost.
  • adsorption separation technology is suitable for the separation of structurally similar substances, such as the separation and purification of low-carbon hydrocarbon gases.
  • existing adsorption materials such as zeolite molecular sieves, activated carbon, polymers, metal-organic framework materials, etc., often find it difficult to accurately identify the slight differences between propylene and propane molecules. They have the disadvantages of low separation selectivity, small adsorption capacity, poor stability, and slow adsorption rate, which restrict the feasibility of propylene/propane adsorption separation technology.
  • Fe-MOF-74 (Science, 2012, 335(6076): 1606-1610) has a high density of unsaturated metal sites, which can generate electrostatic interactions with the ⁇ electrons of the propylene double bond, but due to the large pore size The selectivity for propylene/propane mixed gas is low.
  • propylene propane molecular sieve materials with suitable pore size can greatly improve the separation selectivity of propylene/propane, such as KAUST-7 (Science, 2016, 353: 137-140) and Y-abtc (Advanced Materials, 2018, 30: 1805088), which have suitable pore size and can exclude larger propane molecules while adsorbing smaller propylene molecules.
  • KAUST-7 Science, 2016, 353: 137-140
  • Y-abtc Advanced Materials, 2018, 30: 1805088
  • the current propylene propane screening materials face defects such as low working capacity, slow adsorption rate, and difficult regeneration.
  • the present invention provides a molecular sieve with a point screening structure (which can be recorded as ZU-609), which is composed of 1,2-ethanedisulfonate anions with rigid long strip characteristics, 4,4'-bipyridine sulfide (CAS No. 37968-97-1) with flexible and tortuous characteristics, and metal cation Cu 2+ through coordination bonds.
  • a mixture containing propylene and propane is contacted with the molecular sieve, and the molecular sieve can preferentially adsorb propylene in the mixture to purify propylene to obtain high-purity propylene.
  • a molecular sieve with a point sieving structure formed by connecting 1,2-ethanedisulfonate anion (organic anion), 4,4'-bipyridine sulfide (organic ligand) and Cu 2+ (metal cation) through coordination bonds, with a chemical formula of [MSL 2 ] ⁇ , wherein M represents Cu 2+ , S represents 1,2-ethanedisulfonate anion, L represents 4,4'-bipyridine sulfide, and ⁇ represents that the molecular sieve is formed by spatial expansion of a plurality of structural units constituting MSL 2 ;
  • the molecular sieve with a point screening structure has local point-shaped pore contraction (see FIG. 1 ).
  • organic ligands are coordinated with metal cations through nitrogen atoms, and all organic ligands are di-coordinated; 1,2-ethanedisulfonate anions are coordinated with metal cations through oxygen atoms, and each 1,2-ethanedisulfonate anion is connected to two metal cations; each metal cation is connected to four different organic ligands and coordinated with two oxygen atoms at the same time.
  • the present invention prepares a novel molecular sieve material with a point screening structure by combining metal cations, organic ligands and organic anions, and realizes the precise control of the pore size of the molecular sieve porous material with the point screening structure.
  • propylene and propane molecules come into contact with the molecular sieve porous material ZU-609 with a point screening structure, since propylene has a smaller molecular size than propane, the precisely adjusted material pore size enables propylene to enter the molecular sieve porous material with a point screening structure while excluding propane from entering the pores, thereby showing good size screening characteristics.
  • the high diffusion barrier path formed by the diffusion of propylene molecules in the pores is relatively short (see Figure 3).
  • the 1,2-ethanedisulfonate anion of the present invention can be represented as follows:
  • the molecular sieve with a point screening structure of the present invention has a screening hole window cross-sectional size of Propane size exclusion can be achieved.
  • the flexible and tortuous 4,4'-dipyridyl sulfide ligand and the rigid and long 1,2-ethanedisulfonate anion help to construct the macroporous cavity of the molecular sieve (see Figure 2).
  • the rigid pyridine ring on the ligand molecule creates conditions for the construction of the sieving window.
  • the molecular sieve of the present invention also has The large pores provide enough space to achieve extremely high diffusion coefficient and adsorption capacity of propylene.
  • Propylene can enter the pores of the molecular sieve of the present invention due to its smaller kinetic size, while propane cannot enter the pores of the molecular sieve of the present invention due to its larger kinetic size. Therefore, the molecular sieve of the present invention can achieve efficient adsorption separation of propylene/propane mixed gas.
  • the present invention also provides a method for preparing the molecular sieve with a point sieving structure.
  • a Cu 2+ source, 1,2-ethane disulfonate and 4,4'-dipyridyl sulfide are mixed and reacted in a reaction solvent to obtain the molecular sieve with a point sieving structure.
  • the reaction solvent may be water and/or an organic solvent.
  • the organic solvent may include methanol, etc. If the reaction solvent is water and an organic solvent, the volume ratio of water to the organic solvent may be 1:1-5.
  • the Cu 2+ source may include at least one of chloride, nitric acid compound, and the like.
  • the 1,2-ethanedisulfonate salt may include sodium 1,2-ethanedisulfonate and the like.
  • the usage ratio of the Cu 2+ source to the reaction solvent may be 1 mol:35-45L.
  • the solid and liquid are separated, and the solid is taken to remove the solvent molecules in the pores to obtain the molecular sieve with a point sieving structure.
  • the method of removing the solvent molecules in the pores can be drying by vacuum desorption and/or flowing gas ( N2 and/or rare gas such as He, Ar, etc.) purging.
  • the reaction can be a solvent thermal reaction, an interface diffusion reaction in a dropwise addition process, or a direct room temperature mixing reaction.
  • the invention also provides the use of the molecular sieve with the point screening structure in adsorbing propylene.
  • the propylene adsorption performance of ZU-609 has the following characteristics: the propylene adsorption isotherm shows a linear adsorption isotherm, which is conducive to pressure swing adsorption; the diffusion coefficient of propylene in ZU-609 at room temperature is 10.02 ⁇ 10 -10 cm -2 s -1 ; the adsorption capacity difference between ZU-609 at 0.1 bar and 1 bar is 2.0 mmol g -1 ; the propylene/propane adsorption ratio at 1 bar is 22.
  • the present invention also provides a method for separation of propylene and propane by adsorptive separation, wherein the molecular sieve with a point sieving structure is used as an adsorbent and is contacted with a mixture containing propylene and propane, wherein the adsorbent selectively adsorbs propylene and excludes propane, thereby achieving separation of propylene and propane.
  • the invention can realize efficient separation of propylene and propane under mild operating conditions, and can separate propylene gas with a purity of 97.0% to 99.99% from a mixture containing propylene and propane.
  • the contacting mode of the adsorbent and the mixture containing propylene and propane can be any one or more combinations of fixed bed adsorption, moving bed adsorption and multi-tower pressure swing adsorption.
  • the multi-tower pressure swing adsorption is described as follows:
  • the first adsorption tower is vacuum desorbed by a vacuum pump, and the desorption pressure is controlled to be 0-0.1 bar, and high-purity propylene is obtained at the outlet, with a purity of up to 99.5%; most of the propylene at the outlet is used as the product, and a small amount of propylene is used to complete the reflux replacement of the next cycle;
  • a mixed gas containing propylene and propane enters a fixed bed adsorption column at a set flow rate under a certain adsorption temperature and pressure and contacts with a molecular sieve having a point sieving structure.
  • the adsorption temperature is -30 to 100°C, preferably 25 to 40°C, and the adsorption pressure is 0 to 10 bar, preferably 1 to 5 bar.
  • the adsorption rate of the propane component is slow, and the adsorption amount is lower than that of the propylene component.
  • the propane component preferentially penetrates the fixed bed adsorption column, and propane gas can be directly obtained at the outlet of the adsorption column;
  • the propane component breaks through, continue to introduce the raw gas for adsorption, adsorb for a certain period of time, so that the propylene adsorption front is not less than 2/3 of the bed layer, or when the propylene component breaks through, stop introducing the mixed gas, and use one of the methods of heating, reducing pressure, etc. or a combination of multiple methods for desorption, the desorption temperature is 0-40°C, preferably 30-40°C, and the desorption pressure is 0.01-1bar, preferably 0.01-0.1bar.
  • Use high-purity propylene or product gas purge replacement to further concentrate propylene to obtain propylene gas.
  • the contact adsorption process between the adsorbent and the mixture containing propylene and propane may be temperature swing adsorption and/or pressure swing adsorption.
  • the mixture containing propylene and propane may contain 99.8 vol% to 0.2 vol% propylene, 0.2 vol% to 99.8 vol% propane and 0 to 10 vol% other substances.
  • the volume ratio of propylene: propane: other substances in the mixture containing propylene and propane is 50:40:10.
  • Other substances have little effect on the adsorption and separation performance of propylene/propane by the molecular sieve with a point sieving structure.
  • the other substances may include at least one of methane, oxygen, nitrogen, hydrogen, ethane, and ethylene.
  • the adsorbent After the adsorbent has finished adsorbing propylene, the adsorbent can be desorbed by at least one of reducing pressure, increasing temperature, and purging with inert gas to obtain propylene and regenerate the adsorbent.
  • the purity of the propylene obtained by desorption can be greater than 99.95%.
  • the present invention has the following beneficial effects:
  • the molecular sieve ZU-609 with a point sieving structure used in the present invention has a linear propylene adsorption isotherm, a high pressure swing adsorption capacity (propylene working capacity from 0.1 bar to 1 bar is as high as 2 mmol g -1 , see FIG4 ), a high desorption efficiency, and can be completely regenerated under normal temperature inert gas purge or vacuum decompression conditions.
  • the selectivity of propylene and propane is high, and the molecular sieving of propylene and propane under room temperature conditions is realized.
  • the adsorption capacity ratio of propylene and propane at 1 bar is as high as 22 (see Figure 5).
  • FIG. 1 is a schematic diagram of the point screening pores of the molecular sieve ZU-609 of the present invention and the traditional screening pores.
  • FIG. 2 is a schematic diagram of the structure of the molecular sieve ZU-609 of the present invention.
  • FIG. 5 is an adsorption isotherm diagram of propylene and propane of the molecular sieve ZU-609 of the present invention at 298K.
  • FIG. 6 is a graph showing the diffusion coefficients of the molecular sieve ZU-609 of the present invention and some materials disclosed in the prior art for propylene.
  • FIG. 7 is a penetration curve diagram of Example 2.
  • the molecular sieve porous material ZU-609 with a point sieving structure is filled in a 10 cm long fixed bed adsorption column.
  • a propylene/propane mixed gas (volume ratio 50:50) is passed into the bed at a flow rate of 3.0 mL/min at 25°C and 1 bar for fixed bed adsorption.
  • High-purity propane (greater than 99.999%) gas can be obtained in the outflowing gas.
  • the adsorption is stopped.
  • the adsorption column can be desorbed by purging with 3.0 mL/min nitrogen to obtain propylene gas with a purity greater than 99.5%, and the regeneration of the adsorption column is completed.
  • the breakthrough curve is shown in Figure 7.
  • the molecular sieve porous material ZU-609 with a point sieving structure was filled in a 5cm fixed bed adsorption column, and a propylene/propane mixed gas (volume ratio 40:60) was passed into the bed at a flow rate of 0.5mL/min at 40°C and 5bar for fixed bed adsorption. After a certain period of adsorption, the mixed gas was stopped after the propylene component penetrated. The propylene gas component enriched in the fixed bed was desorbed by decompression at 25°C to 1bar, and propylene gas with a purity of 99.5% was obtained.
  • the molecular sieve porous material ZU-609 with a point screening structure is made into particles and loaded into a fixed bed adsorption column.
  • a propylene/propane/ethylene/ethane mixed gas (volume ratio of 45:45:5:5) is introduced into the bed at 20 mL/min at 100° C. and 10 bar for fixed bed adsorption, and is fully in contact with the adsorbent particles. After adsorption for a certain period of time, the propylene component penetrates, and then the introduction of the mixed gas is stopped.
  • the gas enriched in the adsorbent particles is desorbed by heating to 30° C. and reducing the pressure to 0.1 bar for desorption.
  • the desorbed gas is then circulated into the fixed bed for adsorption, and desorbed after the propylene adsorption is saturated, and propylene gas with a purity greater than 98% is obtained by desorption.
  • the molecular sieve porous material ZU-609 with a point sieving structure is filled in two 100mL fixed bed adsorption columns.
  • Propylene is preferentially adsorbed.
  • the introduction of the mixed gas is stopped.
  • column 1 After the impurity gas that is not adsorbed in column 1 is discharged, column 1 is evacuated to 0.05bar with a vacuum pump to obtain the preliminary product gas and complete the regeneration of column 1 at the same time.
  • the preliminary product gas is introduced into column 2 for adsorption. When the propylene adsorption front reaches about 2/3 of the bed layer, the introduction of the mixed gas is stopped.
  • column 2 After the impurity gas that is not adsorbed in column 2 is discharged, column 2 is evacuated to 0.05bar with a vacuum pump to obtain the product gas and complete the regeneration of column 2 at the same time.
  • Propylene gas with a purity of 99.999% is obtained through two adsorption and desorption processes.

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Abstract

本发明公开了一种具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用。本发明分子筛由1,2-乙烷基二磺酸根阴离子、4,4'-二吡啶硫醚和Cu2+通过配位键连接形成，化学式[MSL2]∞，其中M表示Cu2+，S表示1,2-乙烷基二磺酸根阴离子，L表示4,4'-二吡啶硫醚，∞表示分子筛由若干个组成为MSL2的结构单元在空间拓展而成；本发明分子筛具有局部的点状孔道收缩。制备方法：Cu2+源、1,2-乙烷基二磺酸盐和4,4'-二吡啶硫醚于反应溶剂中混合反应，得到具有点筛分结构的分子筛。本发明具有材料稳定性好、吸附选择性高、吸附容量高、吸附速率高、再生容易等突出优点，具有良好的工业应用前景。

Description

具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用 技术领域
本发明涉及分子筛及化工分离技术领域，具体涉及一种具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用。
背景技术
丙烯作为石油化工的基石，是世界上产量最大的化学品之一，其下游产品主要包括聚丙烯、环氧丙烷、丙烯腈等，广泛应用于塑料、制药、纺织品、涂料等各个国民经济行业。目前工业上丙烯的生产主要从石脑油裂解的低碳烃混合物中分离制备，而低碳烃分离的关键和技术难点在于分子尺寸接近，物理性质相似乙烯/乙烷，丙烯/丙烷的分离。然而，丙烯与丙烷的结构性质高度相似，仅在不饱和度上存在微小差异，使得丙烯/丙烷分离难度大、能耗高。目前，丙烯丙烷的分离技术主要包括低温精馏、溶剂吸收、膜分离和吸附分离等。其中低温精馏技术的发展最为成熟并在工业上广泛使用，但由于丙烯和丙烷的沸点接近，相对挥发度小，需要在较高的压力(～22bar)、极低的温度(～160℃)及大回流比下才能实现分离，且塔板数通常超过150，存在着能耗高、装置投资大等不足。溶剂吸收法不仅存在着有机溶剂污染大的问题，选择性也较低；膜分离法则由于现有膜的选择性低，且膜的制作工艺复杂、成本高等缺点，限制其工业应用。
吸附分离技术作为一种低能耗、环境友好型的分离技术，适用于结构相似物质的分离，例如低碳烃气体的分离纯化。但现有的吸附材料，如沸石分子筛、活性炭、聚合物、金属有机框架材料等，往往很难精确识别丙烯和丙烷分子间的微小差异，存在着分离选择性低、吸附容量小、稳定性差、吸附速率慢等不足，制约了丙烯/丙烷吸附分离技术的可行性。例如，4A分子筛虽然可以实现丙烯和丙烷的分子筛分，但存在着常温下丙烯扩散系数(10-11cm-2s-1)过慢的问题，因此只能在150℃高温下强化丙烯扩散实现丙烯和丙烷的分离(Separation Science and Technology，2010，45：1252-1259)。金属-有机框架材料作为一种新兴的多孔吸附材料，具有比表面积大、孔容高以及孔道易进行化学修饰和孔径可以精确调节等突出优点，然而目前广泛研究的π络合型框架材料对于混合气的分离性能仍有待提高。例如，Fe-MOF-74(Science，2012，335(6076)：1606-1610)具有高密度不饱和金属位点，可与丙烯双键π电子产生静电作用，但由于孔径较大 对丙烯/丙烷混合气的选择性较低。利用丙烯和丙烷的分子尺寸差异，设计具有合适孔径的丙烯丙烷分子筛材料可以大幅提高丙烯/丙烷的分离选择性，例如KAUST-7(Science，2016，353：137-140)和Y-abtc(Advanced Materials，2018，30：1805088)，具有合适的孔径，在吸附尺寸较小的丙烯分子的同时可以排斥尺寸较大的丙烷分子。然而目前的丙烯丙烷筛分材料面临着工作容量低，吸附速率慢、再生困难等缺陷。因此设计制备可实现丙烯丙烷分子筛分，兼具高丙烯吸附容量、高丙烯吸附速率、丙烯容易脱附再生的新型多孔材料对于丙烯、丙烷吸附分离技术的开发至关重要。
发明内容
针对上述技术问题以及本领域存在的不足之处，本发明提供了一种具有点筛分结构的分子筛(可记为ZU-609)，其由具有刚性长条状特征的1,2-乙烷基二磺酸根阴离子、具有柔性可曲折特征的4,4'-二吡啶硫醚(CAS号37968-97-1)以及金属阳离子Cu2+通过配位键构成。将含丙烯丙烷的混合物与所述分子筛进行接触，所述分子筛可优先吸附混合物中的丙烯，实现丙烯纯化得到高纯丙烯。本发明通过对分子筛的孔径和孔道形状进行精确的调控构建了一种点筛分结构的分子筛多孔材料ZU-609，使丙烯高选择性高容量吸附在在孔道中的同时排阻丙烷进入孔道，从而实现高纯丙烯的生产。本发明具有材料稳定性好、吸附选择性高、吸附容量高、吸附速率高、再生容易等突出优点，具有良好的工业应用前景。
一种具有点筛分结构的分子筛，由1,2-乙烷基二磺酸根阴离子(有机阴离子)、4,4'-二吡啶硫醚(有机配体)和Cu2+(金属阳离子)通过配位键连接形成，化学式[MSL2]∞，其中M表示Cu2+，S表示1,2-乙烷基二磺酸根阴离子，L表示4,4'-二吡啶硫醚，∞表示所述分子筛由若干个组成为MSL2的结构单元在空间拓展而成；
所述具有点筛分结构的分子筛具有局部的点状孔道收缩(参见图1)。
在所述具有点筛分结构的分子筛结构中，有机配体通过氮原子与金属阳离子配位，所有有机配体均为二配位；1,2-乙烷基二磺酸根阴离子通过氧原子与金属阳离子配位，每个1,2-乙烷基二磺酸根阴离子连接两个金属阳离子；每个金属阳离子与四个不同的有机配体相连，同时与两个氧原子配位。
本发明通过金属阳离子、有机配体与有机阴离子的组合，制备了新型的具有点筛分结构的分子筛材料，实现点筛分结构的分子筛多孔材料孔径的精确调控。丙烯、丙烷分子与具有点筛分结构的分子筛多孔材料ZU-609接触时，由于丙烯相比丙烷具有更小的分子尺寸，因此，精确调整的材料孔径使丙烯能够进入具有点筛分结构的分子筛多孔材料中的同时排阻丙烷进入孔道，从而表现出良好的尺寸筛分特性。同时，由于本发明分子筛的结构特征，丙烯分子在孔道中扩散形成的高扩散能垒路径较短(参见图3)。
本发明所述的1,2-乙烷基二磺酸根阴离子可表示如下：
本发明所述的具有点筛分结构的分子筛，筛分孔窗截面尺寸为 可实现丙烷尺寸排阻。
具有柔性可曲折特征的4,4'-二吡啶硫醚配体和具有刚性长条状特征的1,2-乙烷基二磺酸根阴离子有助于构建所述分子筛的大孔腔(参见图2)。而配体分子上的刚性吡啶环则为筛分窗口的构建创造条件。
本发明所述分子筛还具有的大孔腔，可提供足够空间实现丙烯极高的扩散系数和吸附容量。
丙烯由于具有较小的动力学尺寸可以进入本发明分子筛孔道，而丙烷由于具有较大的动力学尺寸不能进入本发明分子筛孔道，因此，本发明分子筛可实现高效的丙烯/丙烷混合气吸附分离。
本发明还提供了所述的具有点筛分结构的分子筛的制备方法，Cu2+源、1,2-乙烷基二磺酸盐和4,4'-二吡啶硫醚于反应溶剂中混合反应，得到所述具有点筛分结构的分子筛。
所述反应溶剂可为水和/或有机溶剂。所述有机溶剂可包括甲醇等。若所述反应溶剂为水和有机溶剂，此时水和有机溶剂的体积比可为1:1～5。
所述Cu2+源可包括氯化物、硝酸化合物等中的至少一种。
所述1,2-乙烷基二磺酸盐可包括1,2-乙烷基二磺酸钠等。
所述制备方法中，Cu2+源、1,2-乙烷基二磺酸盐和4,4'-二吡啶硫醚的用量摩尔比可以Cu2+:1,2-乙烷基二磺酸根阴离子:4,4'-二吡啶硫醚计为1:0.5～3:1～5。
Cu2+源与所述反应溶剂的用量比可为1mol:35～45L。
在一实施例中，所述混合反应结束后，固液分离，取固体脱除孔道内的溶剂分子，得到所述具有点筛分结构的分子筛。进一步的，所述脱除孔道内的溶剂分子的方式可为利用真空脱附和/或流动气体(N2和/稀有气体如He、Ar等)吹扫的方式烘干。
所述的具有点筛分结构的分子筛的制备方法，所述反应可以是溶剂热反应，也可以是滴加过程的界面扩散反应，还可以是直接室温混合反应。
本发明还提供了所述的具有点筛分结构的分子筛在吸附丙烯中的应用。
ZU-609丙烯吸附性能具有以下特征：丙烯吸附等温显呈现线性吸附等温线型，有利于变压吸附；常温时丙烯在ZU-609中扩散系数达10.02×10-10cm-2s-1；ZU-609在0.1bar和1bar的之间的吸附容量差达2.0mmol g-1；1bar时的丙烯/丙烷吸附量比达22。
丙烯在本发明所述分子筛孔道中的吸附速率快，所述分子筛在动态分离实验中，可在高丙烯丙烷混合气气速下进行操作。
作为一个总的发明构思，本发明还提供了一种吸附分离丙烯丙烷的方法，以所述的具有点筛分结构的分子筛为吸附剂，与含丙烯和丙烷的混合物接触，所述吸附剂选择性吸附丙烯同时排阻丙烷，实现丙烯和丙烷的分离。
本发明可在温和的操作条件下实现丙烯丙烷的高效分离，可从含丙烯和丙烷的混合物中分离得到纯度为97.0％～99.99％的丙烯气体。
所述吸附剂与所述含丙烯和丙烷的混合物的接触方式可为固定床吸附、移动床吸附、多塔变压吸附中的任意一种或多种组合。
示例的，所述多塔变压吸附介绍如下：
1)含有丙烯、丙烷的混合气体经压缩机加压后在恒定压力下送入第1个吸附塔进行吸附，控制第1个吸附塔内吸附压力为1～10bar，吸附温度为25～40℃，第1个吸附塔的出口处直接富集丙烷，其纯度大于99.9％。
2)对第2个吸附塔进行置换和抽真空操作，其余第3，…，n(n≥3)个吸附塔则进行均压操作；当第1个吸附塔吸附完成时，第2个吸附塔抽真空停止，第1个吸附塔开始对第2个吸附塔进行均压操作；
3)采用上一个循环周期收集到的部分高纯丙烯对第1个吸附塔进行回流置换操作，此时对第n个吸附塔进行产品气快速充压并进入吸附阶段；
4)利用真空泵抽吸的方法对第1个吸附塔进行真空解吸，控制解吸压力为0～0.1bar，出口得到高纯度的丙烯，纯度可达99.5％；出口处的丙烯大部分作为产品，少量丙烯用来完成下一个循环周期的回流置换；
5)准备再次升压进行下一个循环。
示例的，所述固定床吸附介绍如下：
a)含有丙烯、丙烷的混合气体在一定的吸附温度及压力下以设定流速进入固定床吸附柱中与具有点筛分结构的分子筛接触，吸附温度为-30～100℃，优选为25～40℃，吸附压力为0～10bar，优选为1～5bar，丙烷组分吸附速率慢，吸附量低于丙烯组分，丙烷组分优先穿透固定床吸附柱，在吸附柱出口可直接获得丙烷气体；
b)丙烷组分穿透后，继续通入原料气进行吸附，吸附一定时间，使丙烯吸附前沿不低于床层的2/3，或进行至丙烯组分穿透时，停止通入混合气，采用升温、减压等方法中的一种或将多种方法结合进行脱附，脱附温度为0～40℃，优选为30～40℃，脱附压力为0.01～1bar，优选为0.01～0.1bar。采用高纯丙烯或者产品气吹扫置换对丙烯进行进一步提浓，获得丙烯气体。
所述吸附剂与所述含丙烯和丙烷的混合物的接触吸附过程可为变温吸附和/或变压吸附。
所述含丙烯和丙烷的混合物中可含有99.8vol％～0.2vol％的丙烯、0.2vol％～99.8vol％的丙烷以及0～10vol％的其它物质。例如所述含丙烯和丙烷的混合物中丙烯:丙烷:其它物质体积比＝50:40:10。其它物质对具有点筛分结构的分子筛吸附分离丙烯/丙烷性能的影响较小。
所述其它物质可包括甲烷、氧气、氮气、氢气、乙烷、乙烯中的至少一种。
所述吸附剂在完成丙烯吸附后，可采用减压、升温、惰性气体吹扫中的至少一种方式对所述吸附剂进行丙烯解吸，获得丙烯，同时实现所述吸附剂的再生。解吸获得的丙烯纯度可大于99.95％。
本发明与现有技术相比，有益效果有：
1、本发明采用的具有点筛分结构的分子筛ZU-609丙烯吸附等温线为线性，变压吸附容量高(0.1bar到1bar的丙烯工作容量高达2mmol g-1，参见图4)，脱附效率高，可在常温惰性气体吹扫或抽真空减压条件下实现完全再生。
2、丙烯丙烷选择性高，实现了丙烯丙烷常温条件下的分子筛分，1bar下丙烯丙烷的吸附容量比高达22(参见图5)。
3、本发明的具有点筛分结构的分子筛ZU-609与其他丙烯丙烷分子筛材料相比，具有更高丙烯扩散系数(参见图6)，可在高气体流速下进行吸附和脱附。
4、本发明的具有点筛分结构的分子筛多孔材料，采用来源广泛、价格低廉的原料制得，合成条件温和，方法简便，重复性好，具有水、热稳定性好、使用寿命长的优点，同时分离性能受水分、硫化物等影响较小。
5、本发明提供的分离方法，可获得纯度达99.95％以上的丙烯气体。
附图说明
图1为本发明分子筛ZU-609点筛分孔道和传统筛分孔道的示意图。
图2为本发明分子筛ZU-609的结构示意图。
图3为丙烯分子在本发明分子筛ZU-609孔道中扩散形成的扩散能垒路径图。
图4为本发明分子筛ZU-609与现有技术公开的一些材料的变压吸附容量图。
图5为本发明分子筛ZU-609在298K下对丙烯和丙烷的吸附等温线图。
图6为本发明分子筛ZU-609与现有技术公开的一些材料对丙烯的扩散系数图。
图7为实施例2的穿透曲线图。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1
将1mol硝酸铜、1mol 1,2-乙烷基二磺酸钠及1mol 4,4'-二吡啶硫醚共同加入40L甲醇中，在常温下搅拌反应1h。反应结束后，25℃下真空抽滤收集所得固体产品，再在100℃抽真空条件下将样品活化脱除孔道内的客体溶剂分子后获得具有点筛分结构的分子筛多孔材料ZU-609。
ZU-609材料298K对丙烯和丙烷的吸附等温线如图5所示。
实施例2
将具有点筛分结构的分子筛多孔材料ZU-609填装于10cm长的固定床吸附柱中，在25℃、1bar下将丙烯/丙烷混合气(体积比50:50)以3.0mL/min流速通入床层中进行固定床吸附，流出气体中可获得高纯度丙烷(大于99.999％)气体，当丙烯穿透时，停止吸附。在常温下，吸附柱采用3.0mL/min氮气吹扫即可解吸附获得纯度大于99.5％的丙烯气体，并完成吸附柱的再生，穿透曲线如图7所示。
实施例3
将具有点筛分结构的分子筛多孔材料ZU-609产品填装于5cm固定床吸附柱中，在40℃、5bar下将丙烯/丙烷混合气(体积比40:60)以0.5mL/min流速通入床层中进行固定床吸附，吸附一定时间，待丙烯组分穿透后，停止通入混合气。采用在25℃减压到1bar脱附的方式将富集在固定床中的丙烯气组分进行解吸，获得纯度达99.5％的丙烯气体。
实施例4
将具有点筛分结构的分子筛多孔材料ZU-609制成颗粒装于固定床吸附柱，在100℃、10bar下将丙烯/丙烷/乙烯/乙烷混合气(体积比45:45:5:5)以20mL/min通入床层中进行固定床吸附，与吸附剂颗粒充分接触，吸附一定时间后，待丙烯组分穿透后，停止通入混合气，采用升温到30℃减压到0.1bar脱附的方式将富集在吸附剂颗粒中的气体进行解吸，然后将解吸得到的气体循环通入固定床中吸附，并在丙烯吸附饱和后进行脱附，解吸获得纯度大于98％的丙烯气体。
实施例5
将具有点筛分结构的分子筛多孔材料ZU-609填充于50cm长固定床吸附柱中，在5℃、4bar下以100mL/min流速通入含有少量甲烷的丙烯/丙烷混合气(体积比丙烯:丙烷:甲烷＝80:15:5)进行固定床吸附，丙烯优先吸附，在丙烯吸附前沿至床层2/3左右时，停止通入混合气，将吸附柱减压至丙烯刚穿透，通入适量高纯丙烯逆向置换，采用升温到40℃减压到0.5bar脱附的方式将吸附柱中的气体进行解吸，获得纯度达99.99％的丙烯气体，并完成吸附材料的再生。
实施例6
将具有点筛分结构的分子筛多孔材料ZU-609填充于2根100mL固定床吸附柱中，在15℃、6bar下以100mL/min流速向柱1通入含有少量甲烷的丙烯/丙烷混合气(体积比丙烯:丙烷＝99.8:0.2)进行固定床吸附，丙烯优先吸附，在丙烯吸附前沿至床层2/3左右时，停止通入混合气。排出柱1中未被吸附的杂质气体后，对柱1用真空泵抽真空至0.05bar获得初步产品气同时完成柱1的再生。将初步产品气通入柱2进行吸附，在丙烯吸附前沿至床层2/3左右时，停止通入混合气。排出柱2中未被吸附的杂质气体后，对柱2用真空泵抽真空至0.05bar获得产品气同时完成柱2的再生。两次吸脱附过程获得纯度达99.999％的丙烯气体。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种具有点筛分结构的分子筛，其特征在于，由1,2-乙烷基二磺酸根阴离子、4,4'-二吡啶硫醚和Cu2+通过配位键连接形成，化学式[MSL2]∞，其中M表示Cu2+，S表示1,2-乙烷基二磺酸根阴离子，L表示4,4'-二吡啶硫醚，∞表示所述分子筛由若干个组成为MSL2的结构单元在空间拓展而成；
    所述具有点筛分结构的分子筛具有局部的点状孔道收缩。
  2. 根据权利要求1所述的具有点筛分结构的分子筛，其特征在于，所述分子筛的筛分孔窗截面尺寸为所述分子筛具有 的大孔腔。
  3. 根据权利要求1或2所述的具有点筛分结构的分子筛的制备方法，其特征在于，Cu2+源、1,2-乙烷基二磺酸盐和4,4'-二吡啶硫醚于反应溶剂中混合反应，得到所述具有点筛分结构的分子筛。
  4. 根据权利要求3所述的制备方法，其特征在于，所述反应溶剂为水和/或有机溶剂；所述有机溶剂包括甲醇；
    所述Cu2+源包括氯化物、硝酸化合物中的至少一种；
    所述1,2-乙烷基二磺酸盐包括1,2-乙烷基二磺酸钠；
    Cu2+源、1,2-乙烷基二磺酸盐和4,4'-二吡啶硫醚的用量摩尔比以Cu2+:1,2-乙烷基二磺酸根阴离子:4,4'-二吡啶硫醚计为1:0.5～3:1～5；
    Cu2+源与所述反应溶剂的用量比为1mol:35～45L；
    所述混合反应结束后，固液分离，取固体脱除孔道内的溶剂分子，得到所述具有点筛分结构的分子筛。
  5. 根据权利要求1或2所述的具有点筛分结构的分子筛在吸附丙烯中的应用。
  6. 一种吸附分离丙烯丙烷的方法，其特征在于，以权利要求1或2所述的具有点筛分结构的分子筛为吸附剂，与含丙烯和丙烷的混合物接触，所述吸附剂选择性吸附丙烯同时排阻丙烷，实现丙烯和丙烷的分离。
  7. 根据权利要求6所述的方法，其特征在于，所述吸附剂与所述含丙烯和丙烷的混合物的接触方式为固定床吸附、移动床吸附、多塔变压吸附中的任意一种或多种组合。
  8. 根据权利要求6所述的方法，其特征在于，所述吸附剂与所述含丙烯和丙烷的混合物的接触吸附过程为变温吸附和/或变压吸附。
  9. 根据权利要求6所述的方法，其特征在于，所述含丙烯和丙烷的混合物中含有99.8vol％～0.2vol％的丙烯、0.2vol％～99.8vol％的丙烷以及0～10vol％的其它物质；
    所述其它物质包括甲烷、氧气、氮气、氢气、乙烷、乙烯中的至少一种。
  10. 根据权利要求6所述的方法，其特征在于，所述吸附剂在完成丙烯吸附后，采用减压、升温、惰性气体吹扫中的至少一种方式对所述吸附剂进行丙烯解吸，获得丙烯，同时实现所述吸附剂的再生。
PCT/CN2024/137778 2023-12-12 2024-12-09 具有点筛分结构的分子筛及其制备方法和在吸附分离丙烯丙烷中的应用 Pending WO2025124336A1 (zh)

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