CN113908664B - Adsorbent for propylene-propane separation, preparation method thereof and propylene-propane separation method - Google Patents
Adsorbent for propylene-propane separation, preparation method thereof and propylene-propane separation method Download PDFInfo
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Abstract
The invention provides an adsorbent for propylene-propane separation, a preparation method thereof and a propylene-propane separation method. The propylene-propane separation adsorbent is a dispersion liquid and comprises a disperse phase and a dispersing agent, wherein the disperse phase comprises a zeolite imidazole ester framework material, and the dispersing agent comprises water and a hydrophilic solvent. The preparation method of the adsorbent for propylene-propane separation comprises the following steps: mixing water and a hydrophilic solvent, and then adding a zeolite imidazole ester framework material to obtain a dispersion liquid of the zeolite imidazole ester framework material as the propylene-propane separation adsorbent. The propylene-propane separation method uses the above adsorbent for propylene-propane separation to separate propylene-propane mixture gas. The adsorbent for propylene-propane separation provided by the invention is a liquid adsorbent which has high propylene adsorption quantity, high selectivity and good regeneration performance.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to an adsorbent for propylene-propane separation, a preparation method thereof and a propylene-propane separation method.
Background
Propylene is an important basic chemical raw material, and is mainly used for producing polypropylene, and can also be used for producing acrylonitrile, propylene oxide, isopropanol and the like. The main source of propylene is naphtha cracking, however, the production of propylene is often accompanied by the production of propane as a by-product, and thus the extraction of pure propylene from propylene/propane mixtures is of great importance. Propane and propylene have very similar physical properties (boiling points differ by only 5.5K, saturated vapor pressures are close, molecular diameters are close), resulting in propylene/propane separation being one of the most challenging separation tasks worldwide. At present, propylene/propane separation mainly depends on a cryogenic separation method, which is the separation method with highest energy consumption currently, the whole process is carried out at low temperature and high pressure, and 200 trays and a reflux ratio exceeding 15 are needed for completion. Therefore, there is a strong need to develop an efficient and energy-saving separation method to replace the cryogenic separation method.
In recent years, the performance of adsorption in the propylene/propane separation direction has attracted researchers' interest. Adsorbents are a central factor in adsorption processes, and currently available adsorbents for adsorption processes include activated carbon, molecular sieves, and Metal Organic Frameworks (MOFs). Among these adsorbents, MOFs materials are considered to be the most promising adsorbents for efficient propylene/propane separation due to their pore volume size adjustability and functionalization. However, are limited by their respective drawbacks, such as: there is no adsorbent for separating propylene/propane which is directly used in industry at present, but has poor regeneration performance, low propylene adsorption capacity, low selectivity, difficult synthesis and the like.
In addition, the properties of the solid adsorbent also limit the industrial application of MOFs and other materials to propylene/propane separation, and two obvious defects exist in fixed bed adsorption due to the fixed bed operation required by the solid adsorbent. First, in fixed bed adsorption, efficient heat integration is very difficult, and if there is no heat recovery, the energy efficiency of the solid adsorption process will be relatively low. Second, solid adsorbents are typically used in less efficient batch processes and cannot be pumped to flow as liquid adsorbents.
Zeolitic Imidazolate Frameworks (ZIFs) are a subclass of Metal Organic Frameworks (MOFs) and are of great interest in the field of gas separation due to their good hydrothermal and chemical stability and high specific surface area. ZIF-8 is a typical representation of ZIFs materials, and its high porosity and large pore volume make it widely used in the gas adsorption direction. Bohme et al examined the separation effect of ZIF-8 on propylene-propane mixture, and found that although ZIF-8 had a sufficiently high adsorption capacity for both, selectivity was low due to the close adsorption capacity of both.
In the prior art, ZIF-8 zeolite imidazole ester framework material is used as a solid absorbent for separating mixed gas, but because the adsorption capacity of pure solid ZIF-8 zeolite imidazole ester framework material to propylene and propane is very close, the separation of propylene and propane in propylene and propane mixed gas cannot be effectively realized by directly using ZIF-8 zeolite imidazole ester framework material as the solid absorbent. In order to separate propylene from propane in propylene-propane mixed gas, the prior art adopts a ZIF-8 membrane to separate the propylene from the propane in the propylene-propane mixed gas, and the separation of the propylene from the propane in the propylene-propane mixed gas is realized by virtue of the characteristic of different permeabilities of the membrane to different gases, however, the preparation process of the ZIF-8 membrane is complicated, has higher cost and difficult recovery, and is not suitable for large-scale industrial application.
Therefore, developing a propylene propane adsorbent that has a high adsorption capacity, high selectivity, and at the same time is continuously operated and economically viable is one of the greatest challenges in the art.
Disclosure of Invention
The purpose of the present invention is to provide an adsorbent for propylene-propane separation which has a high propylene adsorption amount, high selectivity and good regeneration performance.
In order to achieve the above object, the present invention provides an adsorbent for propylene-propane separation, which is a dispersion liquid comprising a dispersed phase and a dispersant; wherein, the liquid crystal display device comprises a liquid crystal display device,
the disperse phase comprises a zeolite imidazole ester framework material;
the dispersant includes water and a hydrophilic solvent.
The propylene-propane separation adsorbent described above belongs to a liquid adsorbent. In a preferred embodiment, the propylene-propane separation adsorbent is a dispersion of a zeolitic imidazolate framework material formed by dispersing the zeolitic imidazolate framework material in a dispersant.
In the above-mentioned adsorbent for propylene-propane separation, preferably, the adsorbent for propylene-propane separation contains 10% to 30% of the imidazole ester skeleton material and 70% to 90% of the dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation;
in a specific embodiment, the propylene-propane separation adsorbent comprises 10%, 15%, 20%, 25% or 30% of the mass fraction of the imidazolate framework material; preferably 30%;
in a specific embodiment, the propylene propane separation adsorbent comprises 10% of an imidazole ester backbone material and 90% of a dispersant, 15% of an imidazole ester backbone material and 85% of a dispersant, 20% of an imidazole ester backbone material and 80% of a dispersant, 25% of an imidazole ester backbone material and 75% of a dispersant, or 30% of an imidazole ester backbone material and 70% of a dispersant.
In the above adsorbent for propylene/propane separation, preferably, the zeolitic imidazolate framework material is selected from the group consisting of ZIF-8 zeolitic imidazolate framework materials.
In the above-mentioned adsorbent for propylene-propane separation, preferably, the hydrophilic solvent is selected from one or a combination of two or more of ethylene glycol, isohexide and 1, 3-dimethylpropyleneurea; in a specific embodiment, the hydrophilic solvent is ethylene glycol.
In the above-mentioned adsorbent for propylene-propane separation, preferably, the dispersed phase comprises 40% to 80% of water and 20% to 60% of a hydrophilic solvent, based on 100% of the total mass of the dispersant;
in a specific embodiment, the dispersed phase comprises 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60% by mass of hydrophilic solvent; preferably 20%;
in a specific embodiment, the dispersed phase comprises 80% water and 20% hydrophilic solvent, 75% water and 25% hydrophilic solvent, 70% water and 30% hydrophilic solvent, 65% water and 35% hydrophilic solvent, 60% water and 40% hydrophilic solvent, 55% water and 45% hydrophilic solvent, 50% water and 50% hydrophilic solvent, 45% water and 55% hydrophilic solvent, or 40% water and 60% hydrophilic solvent.
In the above-described propylene-propane separation adsorbent, preferably, the dispersant is composed of water and a hydrophilic solvent.
The invention also provides a preparation method of the adsorbent for propylene-propane separation, which comprises the following steps:
mixing water and a hydrophilic solvent, and then adding a zeolite imidazole ester framework material to obtain a dispersion liquid of the zeolite imidazole ester framework material as the propylene-propane separation adsorbent.
The invention also provides a propylene-propane separation method, wherein the propylene-propane separation method is used for propylene-propane mixed gas by using the adsorbent for propylene-propane separation.
In the propylene-propane separation method described above, preferably, the propylene-propane separation is performed at 0 ℃ to 40 ℃.
In the propylene-propane separation method described above, it is preferable that the content of propylene in the propylene-propane mixture is 6mol% to 85mol% based on 100% of the total molar amount of propylene-propane.
In the propylene-propane separation method described above, the volume ratio of the propylene-propane mixture gas to the propylene-propane separation adsorbent is preferably 13 to 21.
In the propylene-propane separation method described above, it is preferable that the absorption time for performing propylene-propane separation is 5min to 240min.
The adsorbent for propylene and propane separation provided by the invention is an adsorbent with a zeolite imidazole ester framework material suspended in a liquid phase, and propylene and propane separation in propylene and propane mixed gas can be effectively realized through adsorption separation of the zeolite imidazole ester framework material suspended in the liquid phase. Compared with the separation of propylene and propane in propylene-propane mixed gas by using ZIF-8 zeolite imidazole ester framework material as a solid absorbent, the separation effect is obviously improved. The invention provides an adsorbent for propylene-propane separation, which has the advantages that the adsorption rate of zeolite imidazole ester framework materials on propylene-propane molecules can be changed, the adsorption rate of the propylene molecules is greatly reduced due to the different properties of gas molecules, and the adsorption rate of the propylene molecules is reduced to a smaller extent, so that the selectivity of propylene-propane can be greatly improved, and the propylene-propane separation process becomes more efficient and energy-saving.
The adsorbent for propylene-propane separation provided by the invention has high propylene adsorption capacity, high propylene/propane selectivity and good regeneration performance. The dynamic separation of propylene and propane in propylene-propane mixed gas with various compositions can be realized.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus used in the thermodynamic equilibrium experiment, kinetic separation experiment, and separation experiment of propylene and propane in propylene-propane mixture.
Fig. 2 is a graph showing comparison of absorption kinetics curves of propylene and propane in the propylene-propane separation adsorbent provided in example 1.
FIG. 3A is a graph showing comparison of absorption kinetics curves of propylene and propane in the propylene-propane separation adsorbent provided in comparative example 1.
FIG. 3B is a graph showing comparison of absorption kinetics curves of propylene and propane in the propylene-propane separation adsorbent provided in comparative example 2.
Reference numerals illustrate:
1-air bath, 2-sapphire kettle, 3-magnetic stirring system, 4-high-pressure blind kettle, 5-raw gas storage bottle and pressure acquisition system 6.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In the invention, when a thermodynamic equilibrium experiment, a kinetic separation experiment and a propylene and propane separation experiment in propylene-propane mixed gas are carried out, the device is shown as a figure 1, and comprises a raw gas storage bottle 5, a high-pressure blind kettle 4 and a sapphire kettle 2 which are sequentially connected, wherein the sapphire kettle 2 is provided with a magnetic stirring system 3, a pressure acquisition system 6 is connected with the high-pressure blind kettle 4 and the sapphire kettle 2 to realize pressure value detection in the high-pressure blind kettle 4 and the sapphire kettle 2, and the high-pressure blind kettle 4 and the sapphire kettle 2 are arranged in an air bath 1.
When the thermodynamic equilibrium experiment, the kinetic separation experiment and the separation experiment of propylene and propane in propylene-propane mixed gas are carried out in the invention, the method specifically comprises the following steps:
before the experiment starts, the sapphire kettle 2 is disassembled, the inside of the sapphire kettle and the stirrer are washed three times by deionized water, the sapphire kettle and the stirrer are wiped dry, and a certain amount of prepared adsorbent is added; then reinstalling the sapphire kettle 2 in the air bath 1, and vacuumizing the sapphire kettle 2; vacuum is pumped to the high-pressure blind kettle 4 and the connected pipeline systemIntroducing raw material gas into the blind kettle to replace residual air, repeating the steps for 3 times, and finally injecting the raw material gas with a certain pressure into the high-pressure blind kettle 4; opening a constant-temperature air bath to set an experimental temperature; when the temperature of the air bath 1 is stable and the pressure in the autoclave 4 is stable at a constant value, the corresponding pressure value p of the autoclave 4 is recorded 1 The method comprises the steps of carrying out a first treatment on the surface of the The connecting valve between the high-pressure blind kettle 4 and the sapphire kettle 2 is slowly opened, so that the gas in the high-pressure blind kettle 4 slowly flows into the sapphire kettle 2, and the connecting valve is closed after a certain pressure is reached. The magnetic stirring system 3 is activated to accelerate the whole sorption process.
If thermodynamic equilibrium experiments are carried out, when the pressure in the sapphire kettle 2 is unchanged and stabilized for 30min, i.e. an equilibrium state is reached, the autoclave 4 (p 2 ) And sapphire pot 2 (p) E ) A medium pressure value; repeating the steps until the equilibrium pressure reaches the experimental requirement.
If a kinetic separation experiment is performed, a prescribed adsorption time is set as t 1 When the predetermined adsorption time was reached, the pressure of the autoclave 4 was recorded as p 2 The pressure of the sapphire kettle 2 is p t1 。
When the pressure of the sapphire pot 2 and the pressure of the autoclave 4 were recorded after the lapse of the predetermined adsorption time, the mixture gas in the sapphire pot 2 was sampled and analyzed for the mixture gas components by using HP7890 gas chromatography.
The molar total amount of gas (n t ) Calculated from the following formula:
wherein T is the temperature of the reaction system; p is p 1 The initial pressure of the high-pressure blind kettle; p is p 2 The pressure of the high-pressure blind kettle after gas injection to the sapphire kettle is balanced; v (V) t The total effective volume of the autoclave and the connecting pipeline is; r is a gas constant; n is n t To the total molar amount of gas injected into autoclave 4; compression factor Z 1 、Z 2 From BWRS equation of state(Benedict-Webb-Rubin-Starling) calculated.
If thermodynamic equilibrium experiments are performed, the amount n of the total material in the equilibrium gas phase in the sapphire kettle E Calculated from the following formula:
wherein p is E The pressure in the sapphire kettle is balanced; z is Z E Is the corresponding compression factor under the temperature and pressure in the sapphire kettle; v (V) g Is the volume of gas phase in the sapphire kettle; t is the temperature of the reaction system; r is a gas constant; n is n E The amount of total gas phase material was equilibrated in the sapphire kettle.
If a kinetic separation experiment is performed, t is reached at a prescribed sorption time 1 In the time of the reaction, the total gas phase material amount n in the sapphire kettle t1 Calculated from the following formula:
wherein p is t1 To achieve the prescribed adsorption time t 1 When in use, the pressure in the sapphire kettle is increased; z is Z t1 Is the corresponding compression factor of the sapphire kettle at the temperature and the pressure at the moment; v (V) g Is the volume of gas phase in the sapphire kettle; t is the temperature of the reaction system; r is a gas constant; n is n t1 To achieve the prescribed adsorption time t 1 And the total gas phase substances in the sapphire kettle.
As for the mixed gas separation experiment, C was adsorbed by the adsorbent 3 H 6 (n 1 ) And C 3 H 8 (n 2 ) Calculated by the following formula:
n 1 ＝n t ×z 1 -n t1 ×y 1
n 2 ＝n t ×z 2 -n t1 ×y 2
wherein z is 1 Is C 3 H 6 Mole fraction in the feed gas; y is 1 Is C when reaching the sorption time 3 H 6 Mole fraction in the mixed gas phase; z 2 Is C 3 H 8 Mole fraction in the feed gas; y is 2 Is C when reaching the sorption time 3 H 8 Mole fraction in the mixed gas phase; n is n t To the total molar amount of gas injected into autoclave 4; n is n t1 To achieve the prescribed adsorption time t 1 When the method is used, the total gas phase substances in the sapphire kettle are in quantity; n is n 1 C sorbed by adsorbent 3 H 6 Molar total amount of gas; n is n 2 C sorbed by adsorbent 3 H 8 Molar sum of gases of (a).
Sorbent sorbed C 3 H 6 Mole fraction (x) 1 ) And C 3 H 8 Mole fraction (x) 2 ) Calculated by the following formula:
wherein n is 1 C sorbed by adsorbent 3 H 6 Molar total amount of gas; n is n 2 C sorbed by adsorbent 3 H 8 Molar total amount of gas; x is x 1 C sorbed by adsorbent 3 H 6 Mole fraction; x is x 2 C sorbed by adsorbent 3 H 8 Mole fraction.
C 3 H 6 Relative to C 3 H 8 The separation factor (β) of (c) is calculated by the following formula:
wherein y is 1 Is C when reaching the sorption time 3 H 6 Mole fraction in the mixed gas phase; y is 2 Is the arrival time at the time of adsorptionTime C 3 H 8 Mole fraction in the mixed gas phase; x is x 1 C sorbed by adsorbent 3 H 6 Mole fraction; x is x 2 C sorbed by adsorbent 3 H 8 Mole fraction; beta is C 3 H 6 Relative to C 3 H 8 Is a separation factor of (a).
C 3 H 6 Solubility S of (2) V The definition is as follows:
V S ＝h×π×r 2
wherein V is S The volume of the adsorbent is calculated by the height h of the adsorbent in the sapphire kettle; r is the inner diameter of the sapphire kettle; h is the height of the adsorbent in the sapphire kettle; n is n 1 C sorbed by adsorbent 3 H 6 Molar total amount of gas; s is S V Is C 3 H 6 Is a solvent for the polymer.
The gas-liquid ratio phi is calculated by the following formula:
wherein phi is the gas-liquid ratio; n is n t To the total molar amount of gas injected into autoclave 4; v (V) S The volume of the adsorbent is calculated by the height h of the adsorbent in the sapphire kettle.
Example 1
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 30 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 70 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80wt% of water and 20wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and ethylene glycol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester skeleton material into the mixed solution of water and ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and ethylene glycol to obtain a ZIF-8 zeolite imidazole ester skeleton material dispersion liquid serving as the propylene propane separation adsorbent.
Based on the adsorbent provided in this example, thermodynamic equilibrium experiments and kinetic separation experiments of pure propylene and pure propane were performed at a temperature of 20 ℃ and an inlet pressure of 150 KPa.
The kinetics of the adsorbent in this example is plotted against pure propylene and pure propane, and the results are shown in figure 2. As can be seen from fig. 2, the amount of adsorption of the two gases in the adsorbent is relatively close, but the adsorption rates are greatly different: when the sorption time was 25min, the propylene sorption had reached 95% of the equilibrium sorption, whereas the propane sorption was only 45% of the equilibrium sorption; when the adsorption time reaches 40min, the propylene reaches the gas-liquid balance in the adsorbent, and the propane can reach the gas-liquid balance state after 240min, and the obvious dynamic difference between the two provides feasibility for the dynamic separation of propylene-propane mixed gas by the adsorbent.
Example 2
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 10 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 90 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80wt% of water and 20wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and ethylene glycol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester skeleton material into the mixed solution of water and ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and ethylene glycol to obtain a ZIF-8 zeolite imidazole ester skeleton material dispersion liquid serving as the propylene propane separation adsorbent.
Example 3
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 20 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 80 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80wt% of water and 20wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and ethylene glycol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester skeleton material into the mixed solution of water and ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and ethylene glycol to obtain a ZIF-8 zeolite imidazole ester skeleton material dispersion liquid serving as the propylene propane separation adsorbent.
Example 4
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 30 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 70 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 60wt% of water and 40wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and ethylene glycol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester skeleton material into the mixed solution of water and ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and ethylene glycol to obtain a ZIF-8 zeolite imidazole ester skeleton material dispersion liquid serving as the propylene propane separation adsorbent.
Example 5
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 30 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 70 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 40wt% of water and 60wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and ethylene glycol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester skeleton material into the mixed solution of water and ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and ethylene glycol to obtain a ZIF-8 zeolite imidazole ester skeleton material dispersion liquid serving as the propylene propane separation adsorbent.
Example 6
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and isohexylene glycol;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 30 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 70 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80wt% of water and 20wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and isohexanediol according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester framework material into the mixed solution of water and isohexanediol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and isohexanediol to obtain a ZIF-8 zeolite imidazole ester framework material dispersion liquid serving as the adsorbent for propylene-propane separation.
Example 7
This example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material dispersion liquid, and a dispersing agent used for the ZIF-8 zeolite imidazole ester framework material dispersion liquid is a mixture of water and 1, 3-dimethylpropyleneurea;
the ZIF-8 zeolite imidazole ester skeleton material dispersion liquid comprises 30 weight percent of ZIF-8 zeolite imidazole ester skeleton material and 70 weight percent of dispersing agent based on 100 percent of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80wt% of water and 20wt% of a hydrophilic solvent based on 100% of the total mass of the dispersant;
the preparation method comprises the following steps:
uniformly mixing water and 1, 3-dimethylpropyleneurea according to a certain proportion, slowly adding the ZIF-8 zeolite imidazole ester framework material into the mixed solution of water and 1, 3-dimethylpropyleneurea, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and 1, 3-dimethylpropyleneurea to obtain ZIF-8 zeolite imidazole ester framework material dispersion liquid serving as the adsorbent for propylene propane separation.
Comparative example 1
This comparative example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material.
And carrying out thermodynamic equilibrium experiments and kinetic separation experiments of pure propylene and pure propane based on the adsorbent provided in the comparative example at the temperature of 20 ℃ and the air inlet pressure of 380 KPa.
The kinetics of the adsorbent in this comparative example with respect to pure propylene and pure propane is shown in fig. 3A. As can be seen from fig. 3A, the adsorption behavior of the two gases on the adsorbent is very similar, with a relatively close adsorption capacity, and at the same time, similar kinetic properties are shown, both reach gas-solid equilibrium at about 20min, and at the same time, a very fast adsorption rate (0-3 min) is shown at the early stage of adsorption.
Comparative example 2
This comparative example provides an adsorbent for propylene-propane separation
The adsorbent is ZIF-8 zeolite imidazole ester framework material.
At 20 ℃ and 150KPa of air inlet pressure, the thermodynamic equilibrium experiment and kinetic separation experiment of pure propylene and pure propane are carried out based on the adsorbent provided by the comparative example.
The kinetics of the adsorbent in this comparative example with respect to pure propylene and pure propane is shown in fig. 3B. As can be seen from fig. 3B, the adsorption behavior of the two gases on the adsorbent is very similar, with a relatively close adsorption capacity, while showing similar kinetic properties, both reaching gas-solid equilibrium at around 10min, while showing a very fast adsorption rate (0-2 min) at the early stage of adsorption.
As can be seen by comparing fig. 2 with fig. 3A and fig. 3B, the pure solid ZIF-8 zeolite imidazole ester framework material cannot efficiently separate propylene-propane mixed gas, both from the thermodynamic and kinetic aspects. The adsorbent provided in example 1 disperses the solid ZIF-8 zeolite imidazole ester framework material in a mixed solution of liquid phase water and ethylene glycol, the mixed solution of water and ethylene glycol can form a layer of compact semi-permeable membrane on the surface of the ZIF-8 zeolite imidazole ester framework material, the existence of the semi-permeable membrane obviously reduces the adsorption rate of the ZIF-8 zeolite imidazole ester framework material in the liquid phase on propylene and propane molecules, and meanwhile, the adsorption rate of the propylene molecules is greatly reduced due to different properties of gas molecules, and the adsorption rate of the propylene molecules is reduced to a smaller extent. Therefore, the adsorbent provided in example 1 can dynamically separate propylene-propane mixed gas, and the method can greatly improve the selectivity of propylene-propane, so that the propylene-propane separation process becomes more efficient and energy-saving.
Example 8
The embodiment provides a propylene-propane separation method, which is carried out by adopting the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
In this example, propylene and propane separation was performed at different adsorption times using the propylene and propane separation adsorbent provided in example 1, and the results are shown in table 1. The experimental temperature was fixed at 293.15K, the initial gas-liquid ratio was fixed at about 19, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixture) was 1:1.
It can be seen from table 1 that as the sorption time increases, the propylene solubility increases and then stabilizes, and the propylene concentration in the gas phase decreases first and then increases and the separation factor increases first and then decreases. The time interval of 20-30min is the optimal time for dynamically separating propylene and propane, and the separation factor reaches about 8.6 in this time interval, and the propylene concentration in the gas phase is reduced to about 20 mol%. It is generally considered that beta >2.0 has adsorption and separation effects, beta >3.0 has industrial application value, and the liquid absorption/adsorption agent has a separation factor of propylene/propane of 8.6 and has wider propylene-propane separation application value.
TABLE 1
Example 9
The embodiment provides a propylene-propane separation method, which is carried out by adopting the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
In this example, propylene-propane separation was performed on propylene-propane mixed gas having different propylene-propane compositions using the propylene-propane separation adsorbent provided in example 1, and the results are shown in table 2. The experimental temperature was fixed at 273.15K, the initial gas-liquid ratio was fixed at about 19, and the sorption time was fixed at 20min.
TABLE 2
| z 1 (mol％) | Φ | P t1 /(bar) | S V (mol/L) | y 1 (mol％) | x 1 (mol％) | β |
| 6.53 | 18.47 | 1.94 | 0.05 | 1.45 | 18.45 | 15.37 |
| 10.86 | 18.64 | 1.85 | 0.08 | 2.52 | 27.26 | 14.51 |
| 20.80 | 18.79 | 1.73 | 0.15 | 5.60 | 44.66 | 13.61 |
| 35.73 | 18.50 | 1.48 | 0.25 | 11.47 | 62.67 | 12.96 |
| 50.04 | 19.22 | 1.28 | 0.36 | 19.73 | 73.67 | 11.38 |
| 59.41 | 18.70 | 1.11 | 0.41 | 26.38 | 80.43 | 11.47 |
| 73.54 | 18.98 | 0.89 | 0.52 | 40.93 | 87.96 | 10.55 |
| 85.04 | 18.96 | 0.75 | 0.59 | 59.67 | 93.80 | 10.23 |
From table 2, it can be seen that the adsorbent has good separation effect on propylene-propane mixed gas composed of different propylene-propane, the separation factors all reach more than 10, and the separation effect on raw material gas with low propylene concentration is better.
In the industrial application, since multistage separation is often required for propylene-propane separation, in other words, effective separation is required for propylene-propane mixed gas with different propylene-propane compositions, and the adsorbent provided in table 2 can be known to have good separation effect for propylene-propane mixed gas with different propylene-propane compositions, so that the adsorbent for propylene-propane separation provided by the invention has industrial multistage separation application prospect.
Example 10
The embodiment provides a propylene-propane separation method, which is carried out by adopting the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
In this example, propylene-propane separation was performed on a propylene-propane mixture gas composed of propylene and propane using the propylene-propane separation adsorbents provided in examples 1, 2 and 3, respectively, and the results are shown in table 3. The experimental temperature was fixed at 293.15K, the initial gas-liquid ratio was fixed at about 19, the adsorption time was fixed at 20min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixture) was 1:1.
As can be seen from Table 3, the adsorbents with different solid contents have a certain separation effect on propylene-propane mixed gas, and as the solid content increases, the separation factor increases, and the separation effect is obviously improved, which indicates that ZIF-8 plays a leading role in the adsorbent.
TABLE 3 Table 3
| Adsorbent source | Solid phase content | Φ | P t1 /(bar) | S V (mol/L) | y 1 (mol％) | x 1 (mol％) | β |
| Example 2 | 10％ | 18.81 | 1.72 | 0.24 | 38.74 | 63.99 | 2.81 |
| Example 3 | 20％ | 18.96 | 1.48 | 0.31 | 28.11 | 69.88 | 5.93 |
| Example 1 | 30％ | 19.12 | 1.37 | 0.34 | 22.44 | 71.32 | 8.60 |
Example 11
The embodiment provides a propylene-propane separation method, which is carried out by adopting the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
In this example, propylene-propane separation was performed on a propylene-propane mixture gas composed of propylene and propane by using the propylene-propane separation adsorbents provided in examples 1, 4 and 5, and the results are shown in table 4. The experimental temperature was fixed at 293.15K, the initial gas-liquid ratio was fixed at about 19, the adsorption time was fixed at 15min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixture) was 1:1.
As can be seen from Table 4, the adsorbents having different liquid phase compositions can separate propylene-propane mixture to some extent, and the higher the content of ethylene glycol in the liquid phase, the lower the separation factor, and the poorer the separation effect. As the viscosity of the adsorbent becomes large due to the increase of the ethylene glycol content, the mass transfer rate becomes low, resulting in a decrease in the difference in the adsorption rates of the two gases, thereby resulting in a deterioration in the kinetic separation effect. Therefore, the effect of controlling the content of ethylene glycol in the liquid phase to be about 20% is optimal.
TABLE 4 Table 4
| Adsorbent source | Ethylene glycol content | Φ | P t1 /(bar) | S V (mol/L) | y 1 (mol％) | x 1 (mol％) | β |
| Example 1 | 20％ | 19.13 | 1.58 | 0.31 | 26.48 | 74.09 | 7.94 |
| Example 4 | 40％ | 20.15 | 1.98 | 0.23 | 38.95 | 69.19 | 3.52 |
| Example 5 | 60％ | 20.20 | 2.20 | 0.18 | 42.54 | 68.75 | 2.97 |
Example 12
The embodiment provides a propylene-propane separation method, which is carried out by adopting the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
In this example, propylene-propane separation was performed on a propylene-propane mixture gas composed of propylene and propane using the propylene-propane separation adsorbents provided in examples 1, 6 and 7, respectively, and the results are shown in table 5. The experimental temperature was fixed at 293.15K, the initial gas-liquid ratio was fixed at about 19, the adsorption time was fixed at 20min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixture) was 1:1.
As can be seen from Table 5, the combination of ethylene glycol, isohexylene glycol, 1, 3-dimethylpropyleneurea and water as liquid phase solvents has good separation effect on propylene-propane mixture, wherein the separation effect brought by the 1, 3-dimethylpropyleneurea as liquid phase solvent is optimal, and the influence of the ethylene glycol and isohexylene glycol as solvents on the separation effect is small.
TABLE 5
Example 13
This example is used to verify the regeneration performance of the propylene-propane separation adsorbent provided in example 1.
The regeneration performance of the adsorbent is an important property, and in order to verify whether the adsorbent for propylene-propane separation provided by the present invention has good regeneration performance, the propylene-propane separation experiment in the propylene-propane mixture was performed based on the adsorbent for propylene-propane separation provided in example 1, and then the adsorbent after the completion of the experiment was desorbed and the propylene-propane separation experiment in the propylene-propane mixture under the same conditions was repeatedly performed using the desorbed adsorbent. The experimental temperature is fixed at 273.15K, the initial gas-liquid ratio is fixed at about 17, the adsorption time is fixed at 20min, the molar concentration ratio of propylene and propane in the propylene-propane mixed gas of the raw material gas is 1:1, the desorption condition is 298.15K, and the vacuum pumping is carried out for 1h, and the result is shown in Table 6.
TABLE 6
| Number of repetitions | Φ | P t1 /(bar) | S V (mol/L) | y 1 (mol％) | x 1 (mol％) | |
| 0 | 17.00 | 1.09 | 0.32 | 18.03 | 73.28 | 12.47 |
| 1 | 16.99 | 1.04 | 0.33 | 17.60 | 71.90 | 11.98 |
| 2 | 16.79 | 1.06 | 0.32 | 19.09 | 72.14 | 10.98 |
| 3 | 16.82 | 1.00 | 0.33 | 17.21 | 71.05 | 11.81 |
| 4 | 17.06 | 1.03 | 0.33 | 17.86 | 71.18 | 11.36 |
| 5 | 16.95 | 1.03 | 0.33 | 17.74 | 71.47 | 11.61 |
As can be seen from Table 6, the solubility of propylene was kept around 0.33mol/L as the number of experiments was accumulated, the concentration of propylene in the gas phase was reduced to about 18mol%, and the separation factor was kept between 11 and 12, which indicates that the adsorbent for propylene-propane separation provided in example 1 had good regeneration performance, and the regeneration conditions were mild and could be repeatedly used for propylene-propane separation in propylene-propane mixture.
Comparative example 3
The comparative example provides a propylene-propane separation method which is carried out in the mode adopted by the propylene-propane separation experiment in the propylene-propane mixed gas.
The comparative example was conducted to separate propylene and propane at different adsorption times by using the adsorbent for separating propylene and propane provided in comparative example 1, and the results are shown in table 7. The experimental temperature was fixed at 293.15K, the initial gas-liquid ratio was fixed at about 19, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixture) was 1:1. When the reaction time reaches 40min, the gas-solid two phases reach thermodynamic equilibrium, belonging to thermodynamic separation; the kinetic separation is carried out when the reaction time is 5 min. As can be seen from Table 7, the adsorbent exhibited a certain propane selectivity at this time, but the separation factor was very low, only around 1.25. The pure ZIF-8 is used for propylene-propane separation experiments, the separation factors are very low no matter how much the adsorption time is, and the separation effect is poor.
TABLE 7
| t(min) | Φ | P t1 /(bar) | S V (mol/L) | y 1 (mol％) | x 1 (mol％) | |
| 5 | 17.94 | 0.121 | 0.35 | 55.07 | 49.44 | 1.25 |
| 40 | 20.56 | 0.101 | 0.41 | 54.87 | 49.67 | 1.23 |
The principles and embodiments of the present invention have been described in detail with reference to specific examples, which are provided to facilitate understanding of the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (5)
1. An adsorbent for propylene-propane separation, which is a dispersion liquid and comprises a disperse phase and a dispersing agent; wherein, the liquid crystal display device comprises a liquid crystal display device,
the disperse phase is zeolite imidazole ester framework material; wherein, the zeolite imidazole ester framework material is ZIF-8 zeolite imidazole ester framework material;
the dispersing agent is water and a hydrophilic solvent;
wherein, based on 100% of the total mass of the adsorbent for propylene-propane separation, the adsorbent for propylene-propane separation comprises 10% -30% of imidazole ester framework material and 70% -90% of dispersing agent;
wherein the dispersant comprises 40% -80% of water and 20% -60% of hydrophilic solvent based on 100% of the total mass of the dispersant;
wherein the hydrophilic solvent is selected from one or more than two of ethylene glycol, isohexide and 1, 3-dimethylpropyleneurea.
2. The process for producing an adsorbent for propylene propane separation as claimed in claim 1, wherein the process comprises:
mixing water and a hydrophilic solvent, and then adding a zeolite imidazole ester framework material to obtain a dispersion liquid of the zeolite imidazole ester framework material as the propylene-propane separation adsorbent.
3. A propylene-propane separation method, wherein the method uses the adsorbent for propylene-propane separation according to claim 1 to separate propylene from propylene-propane mixed gas;
wherein the propylene-propane separation is performed at 0 ℃ to 40 ℃; the absorption time for propylene-propane separation is 5min-240min.
4. The propylene propane separation method according to claim 3, wherein,
in the propylene-propane mixed gas, the content of propylene is 6mol% to 85mol% based on 100% of the total molar amount of propylene-propane.
5. The propylene-propane separation method according to claim 3, wherein the volume ratio of the propylene-propane mixture gas to the propylene-propane separation adsorbent is 13 to 21.
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