WO2017198096A1 - 一种吸附分离丙烯丙炔的方法 - Google Patents

一种吸附分离丙烯丙炔的方法 Download PDF

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WO2017198096A1
WO2017198096A1 PCT/CN2017/083730 CN2017083730W WO2017198096A1 WO 2017198096 A1 WO2017198096 A1 WO 2017198096A1 CN 2017083730 W CN2017083730 W CN 2017083730W WO 2017198096 A1 WO2017198096 A1 WO 2017198096A1
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propyne
metal
framework material
organic
propylene
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French (fr)
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邢华斌
崔希利
杨立峰
鲍宗必
杨启炜
任其龙
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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
    • 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
    • B01J20/22—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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • 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

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  • the invention relates to the technical field of chemical engineering, in particular to a method for adsorbing and separating propylene propyne from a metal-organic framework material.
  • Propylene is the basic raw material for three major synthetic materials.
  • the carbon three fraction obtained by petroleum cracking contains propylene and 1.0% to 7% of propyne. Since the presence of propyne can seriously affect the polymerization of propylene, generally the polymerization grade propylene requires a propyne content of less than 5 ppm, and the newly developed propylene polymerization catalyst requires a propyne content of even less than 1 ppm.
  • the separation and purification of propylene is one of the important tasks of current petrochemical industry. In addition, propyne itself is a widely used chemical, and the separation of propyne is also important.
  • the industry mainly adopts catalytic selective hydrogenation to remove propyne in propylene.
  • the selective hydrogenation process of propyne mainly includes: carbon three-phase catalytic selective hydrogenation, carbon three-phase catalytic selective hydrogenation and catalytic distillation. .
  • Patent 85106117.6 discloses a process employing a single-stage adiabatic trickle bed reactor employing a catalyst with good selectivity.
  • Patent CN102249836A discloses a preparation method of a highly selective propyne hydrogenation catalyst, wherein the active component Pd of the catalyst has a specific crystal plane structure and reaction performance, and can be stably operated for a long period.
  • Patent CN102040446A discloses a catalytic rectification method, which utilizes the characteristics of low propylene concentration in a propylene rectification column to reduce the side reaction probability of propylene conversion to propane and increase the catalytic selectivity.
  • the propyne catalytic hydrogenation technique described above is susceptible to excessive hydrogenation to convert propylene to propane.
  • the propyne hydrogenation catalysts are all noble metals, resulting in high cost, and the catalyst is easily deactivated. Trace water, carbon monoxide, sulfide, carbon tetra, arsenic, etc. will poison the catalyst, so the carbon three-liquid phase hydrogenation process must Strict control of the content of trace compounds in the inlet gas as well as the reaction temperature and pressure results in high costs.
  • the invention provides a method for adsorbing and separating propylene propyne by an anionic metal-organic framework material.
  • the inorganic anion sites in the metal-organic framework materials selectively adsorb propyne, thereby removing propyne in the propylene propyne mixture to a very low level to obtain a propylene gas having a very low propyne content.
  • the present invention can also obtain a higher purity propyne to achieve efficient use of the propyne component.
  • Metal-organic framework materials are a class of highly ordered crystalline materials with high specific surface area and pore volume. The functional group and the pore volume can be adjusted by adjusting the ligand.
  • the metal-organic framework material of the present invention contains an inorganic or organic anion, and can selectively adsorb propyne as a adsorption site and has a high capacity. It has been found that metal-organic framework materials containing inorganic or organic anions exhibit higher propyne selectivity and adsorption capacity than conventional metal-organic framework materials. The weak hydrogen bond interaction between the anion and acetylene is very beneficial to the removal of propyne.
  • the size of the pore size of the metal-organic framework material can be controlled by adjusting the size of the organic ligand, and the three-dimensional structure of the pore can be adjusted through the intercalation structure to further improve the adsorption selectivity and adsorption capacity.
  • a metal-organic framework material for adsorbing and separating propylene propyne comprises the steps of selectively adsorbing propyne in a mixture of propylene propyne by using an anion-containing metal-organic framework material as an adsorbent to obtain a very low propyne content Propylene gas.
  • the propyne content may be 1 ppm or less.
  • the anion-containing metal-organic framework material comprises at least one of the following four categories:
  • the first type of material, the metal ion M1 and the organic ligand L1 coordinate to form a two-dimensional planar structure, and the three-dimensional structure is formed by bridging the inorganic anionic ligand L2.
  • the metal ion M1 is at least one selected from the group consisting of Zn 2+ , Cu 2+ , Ni 2+ , Co 2+ , Mg 2+ , and Al 2+ .
  • the inorganic anionic ligand L2 is at least one selected from the group consisting of SiF 6 2- , TiF 6 2- , SnF 6 2- , ZrF 6 2- and GeF 6 2- .
  • the organic ligand L1 is selected from at least one of the following structures.
  • R is at least one of the groups shown in the following figures.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently H, F, Cl, Br, I, CH 3 , NH 2 , OH, SO 3 H, COOH Or CF 3 .
  • the second type of material is a porous framework material formed of a metal ion M1 (same as above), a bioorganic ligand L3, and an inorganic anionic ligand (L2, supra).
  • M1 metal ion M1
  • L3 bioorganic ligand
  • L2 inorganic anionic ligand
  • the organic ligand L3 is at least one of the following structures.
  • the third type of material, the metal ion M1 (same as above) and the organic ligand L4 are combined by a coordination bond to form a porous framework material, and then coordinated with Mg(X1) 2 to obtain a metal-organic having an organic anion X1 in the channel. Frame material.
  • the organic ligand L4 is at least one of the following structures.
  • the organic anion X1 is one of the following figures.
  • the fourth type of material the metal ion M1 (same as above) and the organic ligand L4 (same as above) are combined by a coordination bond to form a porous framework material, and then oxidized to oxidize the divalent metal ion M1 to trivalent, and introduce an anion X2 and three
  • the valence metal ion M1 is combined to maintain the electrical neutrality of the metal-organic material.
  • the anion X2 is selected from the group consisting of Cl - , Br - , I - , COO - , CH 3 COO - , SCN - , NTf 2 - , BF 4 - , PF 6 - , SiF 6 2- , TiF 6 2- and N(CN) At least one of 2 - .
  • the anion-containing metal-organic framework material is the first type of material, wherein:
  • the metal ion M1 is at least one of Zn 2+ , Cu 2+ , and Ni 2+ ;
  • the inorganic anionic ligand L2 is at least one of SiF 6 2- , TiF 6 2- , and SnF 6 2- ;
  • the organic ligand L1 is at least one of pyrazine, 4,4'-dipyridineacetylene and 4,4'-bipyridine.
  • the three-dimensional frames of the materials can be interpenetrated to form an interpenetrating structure.
  • L2 is SiF 6 2- .
  • the anion-containing metal-organic framework materials have been named by the academic community but are not limited to the SIFSIX series or SIFSIX MOFs, including but not limited to SIFSIX-1-Cu, SIFSIX-2-Cu-i (i stands for interpenetrating structure) , SIFSIX-3-M1;
  • L2 is TiF 6 2- .
  • the anion-containing metal-organic framework materials formed have been titled TIFSIX series or TIFSIX MOFs by the academic community, including but not limited to TIFSIX-1-Cu, TIFSIX-2-Cu-i, TIFSIX-3-M1. It has been found that the preferred first type of material, which has a relatively higher pore volume, exhibits excellent propyne adsorption capacity and selectivity. Such materials can be synthesized by at least one of a well-known coprecipitation method, an interfacial diffusion method, and a solvothermal method.
  • the anion-containing metal-organic framework material is a second type of material, wherein:
  • the metal ion M1 is at least one of Zn 2+ , Cu 2+ , and Ni 2+ ;
  • the bioorganic ligand L3 is adenine
  • the inorganic anionic ligand L2 is at least one of SiF 6 2- and TiF 6 2- .
  • the anion-containing metal-organic framework material is a third type material or a fourth type material, wherein:
  • the metal ion M1 in the porous frame material is at least one of Mg 2+ and Fe 2+
  • the organic ligand L4 is 2,5-dihydroxy terephthalic acid and 4,4′-dihydroxy-3. At least one of 3'-diphthalic acid.
  • Preferred metal-organic framework bodies in the third and fourth types of materials have been partially named by the academic community but are not limited to M1 2 (dobdc) or M1 2 (dobpdc). Such materials can be synthesized by using at least one of the well-known solvothermal method and interfacial diffusion method.
  • the anion-containing metal-organic framework material is a fourth type of material, wherein the anion X2 is at least one selected from the group consisting of Cl - , Br - , I - , COO - , CH 3 COO - .
  • the propyne content is between 50 ppm and 70%.
  • the mixed gas may contain one or more of propene, water, methane, carbon dioxide, carbon monoxide, hydrogen, nitrogen, and the like in addition to propylene propyne. Therefore, the technology provided by the present invention can withstand many impurity gases as compared with conventional catalytic hydrogenation, thereby improving process economy.
  • the invention finds a method for adsorbing and separating propylene propyne by a metal-organic framework material.
  • propane is contained in the mixed gas
  • the propadiene can also be simultaneously adsorbed and removed by the metal-organic framework material proposed by the invention. .
  • the adsorbent of the present invention has a weak physical force between the adsorbent and the propyne, and the desorption and regeneration are easy.
  • the adsorbent is desorbed and regenerated by vacuum desorption, heating vacuum desorption or heating with an inert gas.
  • the temperature during desorption regeneration is 20 to 100 ° C and the pressure is 0-1 atm. If the temperature is too high, propyne is prone to explosion, and if the temperature is too low, the time required for desorption is relatively long.
  • a significant advantage of the present invention is that it has a large propylene removal depth (less than 1 ppm) which is unprecedented in depth.
  • Both vacuum and heating can reduce the adsorption of propyne on the adsorbent, and better desorption can be achieved by the combination of heating and vacuum desorption.
  • the desorption of propyne gives a higher purity, thereby realizing the utilization of propyne.
  • the temperature is 0 to 40 ° C at the time of adsorption separation.
  • the adsorption temperature is higher than 40 ° C, the adsorption amount of propyne in the adsorbent is significantly decreased.
  • the pressure is 0.5 to 10 atm at the time of adsorption separation.
  • the amount of adsorption increases as the pressure increases, but the pressure is too high and the selectivity decreases.
  • the operating pressure in the industry depends on the pressure of the upstream gas.
  • the adsorbent is a particle, a sphere, a rod or a membrane.
  • the separation of propyne and propylene can be carried out by means of membrane separation.
  • an auxiliary material or an auxiliary agent may be added as needed to form a material of a corresponding shape and a predetermined size by mixing/bonding.
  • An anion-containing metal-organic framework material adsorbent is used, which is a highly ordered microporous organic-inorganic hybrid material having a pore diameter of 0.4-1.2 nm.
  • the pore volume is adjustable from 0.1 to 1.2 cm 3 /g.
  • a large number of anionic active sites and their highly ordered spatial arrangement allow for excellent propyne adsorption performance. Thereby having a high propyne selectivity and adsorption capacity;
  • the weak physical interaction between the metal-organic framework material and the propyne is easy to desorb and regenerate.
  • the desorbed propyne gas can be collected;
  • the material can be reused and reused;
  • the separation method proposed by the present invention is the most promising separation and purification technology of propylene propyne, and has obvious commercial implementation value and economic benefit.
  • the adsorbent was packed into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 ° C for the first 220 minutes. A very low propyne content ( ⁇ 1 ppm) of propylene gas was obtained, and adsorption was stopped. The propyne was desorbed under vacuum at 50 °C. The adsorption column can be reused.
  • Example 1 Obtained an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) propylene propyne mixture containing 1000 ppm of carbon dioxide gas was introduced into the adsorption at 1.25 ml/min at room temperature of 25 °C. Column, propylene gas with very low propyne content ( ⁇ 1 ppm) was obtained in the first 210 min, and adsorption was stopped. The propyne was desorbed under vacuum at 30 °C.
  • Example 1 Obtained an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne containing 2000 ppm of water was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 °C. At the first 215 min, a very low propyne content ( ⁇ 1 ppm) of propylene gas was obtained, and adsorption was stopped. The propyne was desorbed under vacuum at 80 °C.
  • Example 1 Obtained an adsorption column (inner diameter: 4.6 mm, length: 50 mm). At room temperature of 40 ° C, a propylene mixed gas containing 1000 ppm of propyne was introduced into the adsorption column at 1.25 ml/min, and a very low propyne content ( ⁇ 1 ppm) was obtained in the first 350 minutes. The propylene gas stops the adsorption. Helium purged the propyne at 60 °C.
  • the adsorbent was loaded into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 ° C.
  • a very low propyne content ( ⁇ 1 ppm) of propylene gas was obtained at 180 min, and adsorption was stopped.
  • the propyne was desorbed under vacuum at 40 °C.
  • the adsorption column can be reused.
  • Example 5 an adsorption column (having an inner diameter of 4.6 mm and a length of 50 mm) was obtained. At room temperature of 20 ° C, a 50/50 (v/v) propylene propyne mixture was introduced into the adsorption column at 1.25 ml/min, and a very low C was obtained in the first 65 minutes. The propylene gas having an alkyne content ( ⁇ 5 ppm) stops adsorption. At 60 ° C, helium purged the propyne to obtain desorption regeneration.
  • Example 5 an adsorption column (having an inner diameter of 4.6 mm and a length of 50 mm) was obtained. At room temperature of 20 ° C, a 90/10 (v/v) propylene propyne mixture was introduced into the adsorption column at 5.0 ml/min, and a very low C was obtained in the first 25 minutes. Propylene gas with alkyne content ( ⁇ 1 ppm) stopped adsorption. At 60 ° C, helium purged the propyne to obtain desorption regeneration.
  • the adsorbent was charged into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 ° C for the first 45 minutes. A propylene gas having a very low propyne content is obtained, and adsorption is stopped. The propyne was desorbed under vacuum at 60 °C.
  • the resulting product was TIFSIX-2-Cu-i (inorganic anion ligand is TiF 6 -), activation of the adsorbent, the adsorbent is charged into an adsorption column (inner diameter 4.6mm, length 50mm), at room temperature 25 °C, the A 99/1 (v/v) propylene propyne mixture was introduced into the adsorption column at 1.25 ml/min, and a very low propyne content ( ⁇ 1 ppm) of propylene gas was obtained for the first 230 minutes to stop adsorption. The propylene was desorbed under vacuum at 50 °C.
  • the adsorbent was loaded into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 ° C for 215 min. A very low propyne content ( ⁇ 1 ppm) of propylene gas was obtained, and adsorption was stopped. The propyne was desorbed under vacuum at 50 °C. The adsorption column can be reused.
  • the adsorbent was loaded into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 30 ° C for the first 50 minutes. A very low propyne content ( ⁇ 20 ppm) of propylene gas was obtained and adsorption was stopped. The propylene was desorbed under vacuum at 50 °C.
  • Tetrahydrofuran and diisopropylamide were removed by stirring for 2 hours, mixed with 125 mg of Mg 2 (dobpdc), and reacted at 80 ° C for 7 days.
  • the product (the third type of material described in the claims) is obtained.
  • activated The adsorbent was loaded into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 90/10 (v/v) mixture of propylene propyne was introduced into the adsorption column at 2.0 ml/min at room temperature of 25 ° C for 30 minutes. A very low propyne content ( ⁇ 25 ppm) of propylene gas was obtained and adsorption was stopped. The propylene was desorbed under vacuum at 30 °C.
  • the adsorbent was packed into an adsorption column (inner diameter: 4.6 mm, length: 50 mm), and a 99/1 (v/v) mixture of propylene propyne was introduced into the adsorption column at 1.25 ml/min at room temperature of 25 ° C for the first 40 minutes. A very low propyne content ( ⁇ 30 ppm) of propylene gas was obtained, and adsorption was stopped. The propylene was desorbed under vacuum at 30 °C.

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Abstract

一种吸附分离丙烯丙炔的方法，包括以含阴离子的金属-有机框架材料为吸附剂，选择性的吸附丙烯丙炔混合气中的丙炔，得到的纯化后的丙烯气体。该方法采用含阴离子的金属-有机框架材料吸附剂，该吸附剂是一类孔径在0.4-1.2nm可调的高度有序微孔类有机-无机杂化材料，孔容在0.1-1.2cm 3/g可调，大量的阴离子活性位点及其高度有序的空间排列使其显示出优异的丙炔吸附性能。从而具有很高的丙炔选择性和吸附容量。

Description

一种吸附分离丙烯丙炔的方法 技术领域
本发明涉及化学工程技术领域，具体涉及一种金属-有机框架材料吸附分离丙烯丙炔的方法。
背景技术
丙烯是三大合成材料的基本原料。工业中，石油裂解分离得到的碳三馏分中含有丙烯和1.0％～7％的丙炔。因为丙炔的存在会严重影响丙烯的聚合过程，一般聚合级丙烯要求丙炔含量小于5ppm，而最新发展的丙烯聚合催化剂要求丙炔的含量甚至低于1ppm。丙烯的分离和纯化是当前石油化工的重要任务之一。此外，丙炔本身也是应用广泛的化学品，丙炔的分离也十分重要。
工业上主要采用催化选择性加氢脱除丙烯中的丙炔，丙炔选择性加氢工艺主要包括：碳三气相催化选择加氢法、碳三液相催化选择加氢法和催化精馏法。
专利85106117.6公开了一种工艺，该工艺采用单段绝热式滴流床反应器，其采用的催化剂具有很好的选择性。专利CN102249836A公开了一种高选择性丙炔加氢催化剂的制备方法，该催化剂的活性组分Pd具有特定的晶面结构和反应性能，可长周期稳定运行。专利CN102040446A公开了采用催化精馏方法，利用丙烯精馏塔釜丙烯浓度低的特点，来降低丙烯向丙烷转化的副反应几率，调高催化选择性。然而，上述所述的丙炔催化加氢技术容易过度加氢，将丙烯转化为丙烷。此外，丙炔加氢催化剂均为贵金属，导致成本很高，同时催化剂容易失活，微量水、一氧化碳、硫化物、碳四、砷等会使催化剂中毒，因此碳三液相加氢工艺中要严格控制进口气的中微量化合物的含量以及反应温度和压力，导致成本很高。
发明内容
本发明提出一种阴离子金属-有机框架材料吸附分离丙烯丙炔的方法。该类金属-有机框架材料中的无机阴离子位点可选择性的吸附丙炔，从而将丙烯丙炔混合气中丙炔脱除到很低的程度，得到极低丙炔含量的丙烯气体。此外，本发明还可以获得较高纯度的丙炔，实现丙炔组分的高效利用。
金属-有机框架材料是一类具有较高比表面积和孔容的高度有序晶体材料。通过调节配体可以调节功能基团及孔径孔容。本发明中的金属-有机框架材料含有无机或有机阴离子，作为吸附位点可以选择性吸附丙炔且容量很高。研究发现，与常规的金属-有机框架材料相比，含无机或有机阴离子的金属-有机框架材料表现出更高的丙炔选择性和吸附容量。阴离子与乙炔之间为弱的氢键相互作用，十分有利于丙炔的脱除。研究发现通过调节有机配体的大小来可控调节金属-有机框架材料孔径的大小，通过穿插结构可调节孔道立体空间结构，进一步提高吸附选择性和吸附容量。
一种金属-有机框架材料吸附分离丙烯丙炔的方法，包括以含阴离子的金属-有机框架材料为吸附剂，选择性的吸附丙烯丙炔混合气中的丙炔，得到极低丙炔含量的丙烯气体。
获得的极低丙炔含量的丙烯气体中，丙炔含量可在1ppm以下。
所述的含阴离子的金属-有机框架材料，包括以下四类中至少一类：
第一类材料，由金属离子M1与有机配体L1配位形成二维平面结构，通过无机阴离子配体L2桥联形成三维结构。
所述金属离子M1选自Zn2+、Cu2+、Ni2+、Co2+、Mg2+和Al2+中的至少一种。
所述无机阴离子配体L2选自SiF6 2-、TiF6 2-、SnF6 2-、ZrF6 2-和GeF6 2-中的至少一种。
所述有机配体L1选自以下结构中的至少一种。
Figure PCTCN2017083730-appb-000001
Figure PCTCN2017083730-appb-000002
其中，R为下图中所示的基团中的至少一种。
Figure PCTCN2017083730-appb-000003
R1，R2，R3，R4，R5，R6，R7，R8各自独立的为H、F、Cl、Br、I、CH3、NH2、OH、SO3H、COOH或CF3。
第二类材料，由金属离子M1(同上)、生物有机配体L3和无机阴离子配体(L2、同上)形成的多孔框架材料。三者可通过配位键和氢键自组装。
所述有机配体L3为以下结构中的至少一种。
Figure PCTCN2017083730-appb-000004
第三类材料，由金属离子M1(同上)和有机配体L4通过配位键结合形成多孔框架材料，之后再与Mg(X1)2进行配位，得到孔道中含有机阴离子X1的金属-有机框架材料。
所述有机配体L4为以下结构中的至少一种。
Figure PCTCN2017083730-appb-000005
所述有机阴离子X1为下图中的一种。
Figure PCTCN2017083730-appb-000006
第四类材料，由金属离子M1(同上)与有机配体L4(同上)通过配位键结合形成多孔框架材料，再经氧化将二价金属离子M1氧化为三价，并引入阴离子X2与三价的金属离子M1结合，以保持金属-有机材料的电中性。
阴离子X2选自Cl-、Br-、I-、COO-、CH3COO-、SCN-、NTf2 -、BF4 -、PF6 -、SiF6 2-、TiF6 2-和N(CN)2 -中的至少一种。
含阴离子的金属-有机框架材料为第一类材料，其中：
金属离子M1为Zn2+、Cu2+和Ni2+中的至少一种；
无机阴离子配体L2为SiF6 2-、TiF6 2-、SnF6 2-中的至少一种；
有机配体L1为吡嗪、4,4’-二吡啶乙炔、4,4’-联吡啶中的至少一种。
选用第一类材料时，该类材料的三维框架可以相互穿插形成互穿结构。
作为进一步的优选，L2为SiF6 2-。形成的含阴离子的金属-有机框架材料已被学术界冠名为但不限于SIFSIX系列或SIFSIX MOFs，包括但不限于SIFSIX-1-Cu，SIFSIX-2-Cu-i(i代表互穿结构)，SIFSIX-3-M1；
作为进一步的优选，L2为TiF6 2-。形成的含阴离子的金属-有机框架材料已被学术界冠名为TIFSIX系列或TIFSIX MOFs，包括但不限于TIFSIX-1-Cu，TIFSIX-2-Cu-i，TIFSIX-3-M1。研究发现，优选的第一类材料，具有相对更高的孔容，表现出优秀的丙炔吸附容量和选择性。该类材料可采用众所周知的共沉淀法、界面扩散法、溶剂热法中的至少一种予以合成。
含阴离子的金属-有机框架材料为第二类材料，其中：
金属离子M1为Zn2+、Cu2+和Ni2+中的至少一种；
生物有机配体L3为腺嘌呤；
无机阴离子配体L2为SiF6 2-和TiF6 2-中的至少一种。
优选的第二类材料中，部分已被学术界冠名为但不限于MPM-1-TIFSIX。该类材料可采用众所周知的界面扩散法、溶剂热法中的至少一种予以合成。
含阴离子的金属-有机框架材料为第三类材料或第四类材料，其中：
所述多孔框架材料中的金属离子M1为Mg2+、Fe2+中的至少一种，有机配体L4为2,5-二羟基对苯二甲酸、4,4’-二羟基-3,3’-二苯二甲酸中的至少一种。
优选的第三、四类材料中金属-有机框架本体，部分已被学术界冠名为但不限于M12(dobdc)或M12(dobpdc)。该类材料可采用众所周知的溶剂热法、界面扩散法中的至少一种予以合成。
含阴离子的金属-有机框架材料为第四类材料，其中所述阴离子X2选自Cl-、Br-、I-、COO-、CH3COO-中的至少一种。
所述丙烯丙炔混合气中，丙炔含量在50ppm到70％之间。
混合气中除丙烯丙炔以外，还可含有丙二烯、水、甲烷、二氧化碳、一氧化碳、氢气、氮气等其他气体中的一种或多种。因此与传统的催化加氢相比，本发明所提供的技术可以耐受很多杂质气体，从而提高过程经济性。
研究发现所述的一种金属-有机框架材料吸附分离丙烯丙炔的方法，当混合气中含有丙二烯时，丙二烯也可被本发明所提的金属-有机框架材料同时吸附脱除。
本发明吸附剂与丙炔之间为弱的物理作用力，脱附再生容易。所述吸附剂采用真空解吸、加热真空解吸或加热通惰性气体进行解吸再生。
作为优选，解吸再生时温度为20～100℃，压力为0-1atm。如果温度过高，丙炔容易发生爆炸，温度过低，则解吸所需时间相对较长。
本发明的一个突出优点是具有很大的丙烯脱除深度(低于1ppm)，该脱除深度前所未有。真空和加热都能降低丙炔在吸附剂上的吸附，加热和真空解吸协同时可达到更好的脱附效果。解吸得到丙炔具有较高纯度，从而实现丙炔的利用。
作为优选，吸附分离时，温度为0～40℃。
吸附温度如高于40℃，则丙炔在吸附剂的吸附量明显下降。
作为优选，吸附分离时，压力为0.5～10atm。
吸附量随着压力的升高而增大，但压力过高，选择性下降。但工业上的操作压力取决于上游气体的压力。
所述吸附剂为颗粒、球形、棒状或膜。
如果制成膜，可以采用膜分离的方式进行丙炔和丙烯的分离。制成其他形状时可根据需要添加辅料或助剂通过混合/粘合成型，制成相应形状和预定尺寸的材料。
本发明的突出优点是：
1)采用含阴离子的金属-有机框架材料吸附剂，该吸附剂是一类孔径在0.4-1.2nm可调的高度有序微孔类有机-无机杂化材料。孔容在0.1-1.2cm3/g可调。大量的阴离子活性位点及其高度有序的空间排列使其显示出优异的丙炔吸附性能。从而具有很高的丙炔选择性和吸附容量；
2)金属-有机框架材料与丙炔之间为弱的物理作用力，脱附再生容易，本发明中金属-有机框架材料脱附再生过程中，可以收集脱附的丙炔气体；同时，该材料可再生重复使用；
3)丙炔脱除深度大，经吸附后的丙烯气体中丙炔含量小于1ppm，可满足最为严格的下游聚合级丙烯生产的工业需求。
因此，本发明提出的分离方法是目前最具有潜力的丙烯丙炔分离纯化技术，具有明显的商业实施价值和经济效益。
附图说明
图1为实施例1中99/1(v/v)的丙烯丙炔混合气在SIFSIX-2-Cu-i上的穿透曲线。
图2为实施例5中99/1(v/v)的丙烯丙炔混合气在SIFSIX-1-Cu上的穿透曲线
具体实施方式
实施例1
称取46.44毫克4,4’-二吡啶基乙炔(有机配体L1)溶于4ml甲醇中，称取89毫克Cu(BF4)2·xH2O(金属离子M1)和45.96毫克(NH4)2SiF6(无机阴离子配体L2)溶于4ml水中，将上述两种溶液搅拌下混合，然后加热到40-100℃反应12-36小时。将得到的产物SIFSIX-2-Cu-i(无机阴离子配体为SiF6 -)过滤用甲醇洗涤，然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前220min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在50℃下，抽真空脱附丙炔。吸附柱可重复使用。
实施例2
实施例1获得吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将含有1000ppm的二氧化碳气体的99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前210min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在30℃下，抽真空脱附丙炔。
实施例3
实施例1获得吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将含有2000ppm的水分的99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前215min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在80℃下，抽真空脱附丙炔。
实施例4
实施例1获得吸附柱(内径4.6mm，长度50mm)，在室温40℃下，含1000ppm丙炔的丙烯混合气以1.25ml/min通入吸附柱，前350min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在60℃下，氦气吹扫丙炔。
实施例5
称取0.35克4,4’-联吡啶(有机配体L1)溶于乙二醇中。称量0.28克Cu(BF4)2·xH2O(金属离子M1)和0.199克(NH4)2SiF6(无机阴离子配体L2)溶于去离子水中加入到4,4’-联吡啶乙二醇溶液中。在低于100℃条件下搅拌反应2-8小时。将反应得到的紫色粉末产物SIFSIX-1-Cu(无机阴离子配体为SiF6 -)过滤，然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度为50mm)，在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25 ml/min通入吸附柱，前180min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在40℃下，抽真空脱附丙炔。吸附柱可重复使用。
实施例6
实施例5获得吸附柱(内径4.6mm，长度50mm)，在室温20℃下，50/50(v/v)丙烯丙炔混合气以1.25ml/min通入吸附柱，前65min获得极低丙炔含量(<5ppm)的丙烯气体，停止吸附。在60℃下，氦气吹扫丙炔得到解吸再生。
实施例7
实施例5获得吸附柱(内径4.6mm，长度50mm)，在室温20℃下，90/10(v/v)丙烯丙炔混合气以5.0ml/min通入吸附柱，前25min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在60℃下，氦气吹扫丙炔得到解吸再生。
实施例8
称取1mmol的Ni(NO3)2，(金属离子M1)1mmol的(NH4)2SiF6(无机阴离子配体L2)以及2mmol吡嗪(有机配体L1)溶于20mL甲醇，60-80℃搅拌反应2-4天。得到的产物SIFSIX-3-Ni(无机阴离子配体为SiF6 -)，吸附剂活化。将吸附剂装入到吸附柱(内径4.6mm，长度50mm),在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前45min获得极低丙炔含量的丙烯气体，停止吸附。在60℃下，抽真空脱附丙炔。
实施例9
称取46毫克4,4’-二吡啶基乙炔(有机配体L1)溶于4ml甲醇中，称取89毫克Cu(BF4)2·xH2O和61毫克(NH4)2TiF6(无机阴离子配体L2)溶于水中，85℃加热搅拌混合，反应12小时。将得到的产物TIFSIX-2-Cu-i(无机阴离子配体为TiF6 -)，活化吸附剂，将吸附剂装入到吸附柱(内径4.6mm，长度50mm),在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前230min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在50℃下，抽真空脱附丙烯。
实施例10
称取46.44毫克4,4’-二吡啶基乙炔(有机配体L1)溶于4ml甲醇中，称取89毫克Cu(BF4)2·xH2O(金属离子M1)和69.18毫克(NH4)2SnF6(无机阴离子配体L2)溶于水中，将上述两种溶液搅拌下混合，然后加热到40-100℃反应12-36小时。将得到的产物SNFSIX-2-Cu-i(无机阴离子配体为SnF6 -)过滤用甲醇洗涤，然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前215min获得极低丙炔含量(<1ppm)的丙烯气体，停止吸附。在50℃下，抽真空脱附丙炔。吸附柱可重复使用。
实施例11
室温下，称取20.5毫克腺嘌呤(有机配体L3)溶于乙腈水(1:1)溶液中，称取17.6毫克Cu(NO3)2·2.5H2O(金属离子M1)和15.0毫克(NH4)2TiF6(无机阴离子配体L2)溶于水中。先将上述水溶液加入试管中，将含腺嘌呤的乙腈水溶液缓慢加入试管中。界面反应4天后得到紫色晶体MPM-1-TIFSIX(权利要求书所述第二类材料)。然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度50mm)，在室温30℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前50min获得极低丙炔含量(<20ppm)的丙烯气体，停止吸附。在50℃下，抽真空脱附丙烯。
实施例12
0.59克2,5-二羟基苯-1,4-二羧酸(有机配体L4)和0.24克Mg(NO3)2·9H2O(金属离子M1)溶于二甲基甲酰胺：乙醇：水混合溶液中。在120摄氏度反应。收集得到产物Mg2(dobpdc)，在二甲基甲酰胺中浸泡4天。180摄氏度真空干燥。在氮气气氛中将1.94克4-三氟甲基苯酚(有机阴离子X1)溶于无水三甘醇中，滴加8.57毫升含双(二异丙基)酰胺的四氢呋喃溶液。搅拌2小时候将四氢呋喃和二异丙基酰胺除去，与125毫克Mg2(dobpdc)混合，在80摄氏度反应7天。得到产物(权利要求书所述第三类材料)。然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将90/10(v/v)的丙烯丙炔混合气以2.0ml/min通入吸附柱，前30min获得极低丙炔含量(<25ppm)的丙烯气体，停止吸附。在30℃下，抽真空脱附丙烯。
实施例13
2.85克无水FeCl2(金属离子M1)，1.85克2,5-二羟基苯-1,4-二羧酸(有机配体L4)，400毫升DMF，50毫升无水甲醇加入到反应器中。120摄氏度搅拌反应24小时得到黄绿色产物。除去溶剂，加入新鲜无水DMF。DMF洗涤几次后用甲醇洗。然后在250摄氏度下真空干燥24小时得到Fe2(dobpdc)。在手套箱内，13.8毫克的Fe2(dobpdc)加入到乙腈中搅拌。26毫克C12H8S2·PF6 -(阴离子X2)溶于4毫升MeCN中。然后将C12H8S2·PF6 -缓慢滴加，密封后在室温反应15-24小时得到产物，Fe2(dobpdc)(PF6)1.56～5.1MeCN(权利要求书所述第四类材料)，然后活化。将吸附剂装填入吸附柱(内径4.6mm，长度50mm)，在室温25℃下，将99/1(v/v)的丙烯丙炔混合气以1.25ml/min通入吸附柱，前40min获得极低丙炔含量(<30ppm)的丙烯气体，停止吸附。在30℃下，抽真空脱附丙烯。
以上所述仅为本实用新型专利的具体实施案例，但本实用新型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实用新型的领域内，所作的变化或修饰皆涵盖在本实用新型的专利范围之中。

Claims (10)

  1. 一种金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，包括以含阴离子的金属-有机框架材料为吸附剂，选择性的吸附丙烯丙炔混合气中的丙炔，得到极低丙炔含量的丙烯气体。
  2. 如权利要求1所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，所述的含阴离子的金属-有机框架材料，包括以下四类中至少一类：
    第一类材料，由金属离子M1与有机配体L1配位形成二维平面结构，通过无机阴离子配体L2桥联形成三维结构；
    所述金属离子M1选自Zn2+、Cu2+、Ni2+、Co2+、Mg2+和Al2+中的至少一种；
    所述无机阴离子配体L2选自SiF6 2-、TiF6 2-、SnF6 2-、ZrF6 2-和GeF6 2-中的至少一种；
    所述有机配体L1选自以下结构中的至少一种：
    Figure PCTCN2017083730-appb-100001
    其中，R为下图中所示的基团中的至少一种：
    Figure PCTCN2017083730-appb-100002
    R1，R2，R3，R4，R5，R6，R7，R8各自独立的为H、F、Cl、Br、I、CH3、NH2、OH、SO3H、COOH或CF3；
    第二类材料，由金属离子M1、生物有机配体L3和无机阴离子配体L2形成的多孔框架材料；
    所述有机配体L3为以下结构中的至少一种：
    Figure PCTCN2017083730-appb-100003
    第三类材料，由金属离子M1和有机配体L4通过配位键结合形成多孔框架材料，之后再与Mg(X1)2进行配位，得到孔道中含有机阴离子X1的金属-有机框架材料；
    所述有机配体L4为以下结构中的至少一种：
    Figure PCTCN2017083730-appb-100004
    所述有机阴离子X1为下图中的一种：
    Figure PCTCN2017083730-appb-100005
    第四类材料，由金属离子M1与有机配体L4通过配位键结合形成多孔框架材料，再经氧化将二价金属离子M1氧化为三价，并引入阴离子X2与三价的金属离子M1结合；
    阴离子X2选自Cl-、Br-、I-、COO-、CH3COO-、SCN-、NTf2 -、BF4 -、PF6 -、SiF6 2-、TiF6 2-和N(CN)2 -中的至少一种。
  3. 如权利要求2所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，含阴离子的金属-有机框架材料为第一类材料，其中：
    金属离子M1为Zn2+、Cu2+和Ni2+中的至少一种；
    无机阴离子配体L2为SiF6 2-、TiF6 2-、SnF6 2-中的至少一种；
    有机配体L1为吡嗪、4,4’-二吡啶乙炔、4,4’-联吡啶中的至少一种。
  4. 如权利要求3所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，L2为SiF6 2-或TiF6 2-。
  5. 如权利要求2所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，含阴离子的金属-有机框架材料为第二类材料，其中：
    金属离子M1为Zn2+、Cu2+和Ni2+中的至少一种；
    生物有机配体L3为腺嘌呤；
    无机阴离子配体L2为SiF6 2-和TiF6 2-中的至少一种。
  6. 如权利要求2所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，含阴离子的金属-有机框架材料为第三类材料或第四类材料，其中：
    所述多孔框架材料中的金属离子M1为Mg2+、Fe2+中的至少一种，有机配体L4为2,5-二羟基对苯二甲酸、4,4’-二羟基-3,3’-二苯二甲酸中的至少一种。
  7. 如权利要求2所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，含阴离子的金属-有机框架材料为第四类材料，其中所述阴离子X2选自Cl-、Br-、I-、COO-、CH3COO-中的至少一种。
  8. 如权利要求1所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，获得的丙烯气体中丙炔含量低于1ppm，所述吸附剂采用真空解吸、加热真空解吸或加热通惰性气体进行解吸再生。
  9. 如权利要求1所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，吸附分离时，温度为0～40℃。
  10. 如权利要求9所述的金属-有机框架材料吸附分离丙烯丙炔的方法，其特征在于，吸附分离时，压力为0.5～10atm。
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