CN113908664A - 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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- CN113908664A CN113908664A CN202111181042.6A CN202111181042A CN113908664A CN 113908664 A CN113908664 A CN 113908664A CN 202111181042 A CN202111181042 A CN 202111181042A CN 113908664 A CN113908664 A CN 113908664A
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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 adsorbent for separating propylene and propane is dispersion liquid and comprises a dispersion phase and a dispersing agent, wherein the dispersion 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 separating propylene and propane comprises the following steps: mixing water and a hydrophilic solvent, and then adding a zeolite imidazolate framework material to obtain a dispersion liquid of the zeolite imidazolate framework material as the propylene-propane separation adsorbent. The propylene-propane separation method uses the adsorbent for propylene-propane separation to separate propylene-propane mixed gas. The adsorbent for propylene-propane separation provided by the invention is a liquid adsorbent, and has high propylene adsorption capacity, 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, 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, propylene production is often accompanied by the production of propane as a by-product, and therefore the extraction of pure propylene from propylene/propane mixtures is of great importance. Propane and propylene have very similar physical properties (boiling points differ only by 5.5K, saturated vapor pressures are close, molecular diameters are close), resulting in propylene/propane separation being one of the most challenging separation tasks in the world. At present, the separation of propylene/propane mainly depends on a cryogenic separation method, which is the separation method with highest energy consumption at present, and the whole process is carried out at low temperature and high pressure, and 200 trays and a reflux ratio of more than 15 are required to be completed. Therefore, there is an urgent need to develop an efficient and energy-saving separation method to replace the cryogenic separation method.
In recent years, the expression of adsorption in the direction of propylene/propane separation has attracted the interest of researchers. Adsorbents are the core factor in adsorption processes, and currently, adsorbents that can be used in adsorption processes are activated carbon, molecular sieves, and metal organic framework Materials (MOFs). Among these adsorbents, the MOFs materials are considered to be the most promising adsorbents for the efficient separation of propylene/propane due to their tunable pore volume size and functionalization. However, are limited by their respective disadvantages, such as: poor regeneration performance, low propylene adsorption capacity, low selectivity, difficult synthesis and the like, and at present, no adsorbent for separating propylene/propane, which can be directly applied to industry, exists.
In addition, the nature of the solid adsorbent itself limits the industrial application of materials such as MOFs to propylene/propane separation, since the solid adsorbent requires a fixed bed operation, and there are two significant drawbacks in fixed bed adsorption. First, in fixed bed adsorption, efficient heat integration is very difficult, and without heat recovery, the energy efficiency of the solid adsorption process would be low. Second, solid adsorbents are typically used in less efficient batch processes, and cannot be pumped to transport the flow as liquid absorbents do.
Zeolitic imidazolate framework materials (ZIFs) are a subclass of metal organic framework Materials (MOFs), and due to their good hydrothermal and chemical stability and high specific surface area, ZIFs have gained wide attention in the gas separation field. 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 effect of ZIF-8 on separating a propylene-propane mixture and found that ZIF-8 had a sufficiently high adsorption capacity for both gases, but the selectivity was very low because the adsorption capacities were relatively close to each other.
In the prior art, a ZIF-8 zeolite imidazolate framework material is used as a solid absorbent to separate mixed gas, but the adsorption capacity of pure solid ZIF-8 zeolite imidazolate framework material to propylene propane is very close, so that the separation of propylene and propane in propylene propane mixed gas cannot be effectively realized by directly using the ZIF-8 zeolite imidazolate framework material as the solid absorbent. In order to realize the separation of propylene and propane in the propylene-propane mixed gas, in the prior art, a ZIF-8 membrane is adopted to separate propylene and propane in the propylene-propane mixed gas, and the separation of propylene and propane in the propylene-propane mixed gas is realized by means of the characteristics of different permeabilities of different gases by the membrane, however, the preparation process of the ZIF-8 membrane is complicated, high in cost and difficult to recover, and is not suitable for large-scale industrial application.
Therefore, the development of a propylene propane adsorbent with high adsorption capacity and high selectivity, which can be operated continuously and is economically applicable, has become one of the biggest challenges in the field.
Disclosure of Invention
The invention aims to provide an adsorbent for separating propylene from propane, which has high propylene adsorption capacity, high selectivity and good regeneration performance.
In order to achieve the above object, the present invention provides an adsorbent for separating propylene and propane, wherein the adsorbent for separating propylene and propane is a dispersion liquid comprising a dispersion phase and a dispersant; wherein the content of the first and second substances,
the dispersed phase comprises a zeolitic imidazolate framework material;
the dispersant includes water and a hydrophilic solvent.
The above-mentioned adsorbent for separating propylene from propane belongs to a liquid adsorbent. In a preferred embodiment, the adsorbent for propylene propane separation is a zeolite imidazolate framework material dispersion liquid in which a zeolite imidazolate framework material is dispersed in a dispersant.
In the above adsorbent for separating propylene from propane, it is preferable that the adsorbent for separating propylene from propane comprises 10% to 30% of an imidazole ester skeleton material and 70% to 90% of a dispersant, based on 100% of the total mass of the adsorbent for separating propylene from propane;
in a specific embodiment, the adsorbent for propylene propane separation comprises an imidazate framework material in a mass fraction of 10%, 15%, 20%, 25% or 30%; preferably 30%;
in a specific embodiment, the adsorbent for propylene propane separation comprises 10% of an imidazolate framework material and 90% of a dispersant, 15% of an imidazolate framework material and 85% of a dispersant, 20% of an imidazolate framework material and 80% of a dispersant, 25% of an imidazolate framework material and 75% of a dispersant, or 30% of an imidazolate framework material and 70% of a dispersant.
In the above adsorbent for separating propylene from propane, preferably, the zeolitic imidazolate framework material is a ZIF-8 zeolitic imidazolate framework material.
In the above-mentioned adsorbent for separating propylene from propane, the hydrophilic solvent is preferably one or a combination of two or more selected from the group consisting of ethylene glycol, isohexyl glycol and 1, 3-dimethylpropylene urea; in one embodiment, the hydrophilic solvent is ethylene glycol.
In the above 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 the 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-mentioned adsorbent for propylene propane separation, preferably, the dispersant is composed of water and a hydrophilic solvent.
The invention also provides a preparation method of the adsorbent for separating propylene and propane, which comprises the following steps:
mixing water and a hydrophilic solvent, and then adding a zeolite imidazolate framework material to obtain a dispersion liquid of the zeolite imidazolate framework material as the propylene-propane separation adsorbent.
The invention also provides a propylene-propane separation method, wherein the method uses the adsorbent for separating propylene from propane to separate propylene from propane mixed gas.
In the above propylene propane separation process, preferably, the propylene propane separation is carried out at 0 ℃ to 40 ℃.
In the above propylene-propane separation method, it is preferable that the content of propylene in the propylene-propane mixed gas is 6 mol% to 85 mol% based on the total molar amount of propylene-propane taken as 100%.
In the above propylene-propane separation method, the volume ratio of the propylene-propane mixture gas to the propylene-propane separation adsorbent is preferably from 13 to 21.
In the above propylene-propane separation method, the adsorption time for propylene-propane separation is preferably 5min to 240 min.
The adsorbent for separating propylene and propane provided by the invention is an adsorbent with a zeolite imidazole ester framework material suspended in a liquid phase, and can effectively separate propylene from propane in a propylene-propane mixed gas by performing adsorption separation through 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 simply using a ZIF-8 zeolite imidazolate framework material as a solid absorbent, the separation effect is obviously improved. The existence of the liquid phase of the adsorbent for separating propylene from propane provided by the invention can change the adsorption rate of the zeolite imidazole ester framework material to propylene propane molecules, and the adsorption rate of the propane molecules is greatly reduced due to different properties of gas molecules, while the degree of reduction of the adsorption rate of the propylene molecules is smaller, so that the selectivity of propylene and propane can be greatly improved, and the separation process of propylene and propane becomes more efficient and energy-saving.
The adsorbent for separating propylene from propane provided by the invention has the advantages of high propylene adsorption capacity, high propylene/propane selectivity and good regeneration performance. The kinetic separation of propylene and propane in propylene-propane mixed gas with various compositions can be realized.
Drawings
FIG. 1 is a schematic structural diagram of a device used for thermodynamic equilibrium experiments, kinetic separation experiments and experiments for separating propylene from propane in a propylene-propane mixed gas in the invention.
FIG. 2 is a graph showing a comparison of sorption kinetics curves of propylene and propane in the adsorbent for propylene-propane separation provided in example 1.
Fig. 3A is a graph comparing sorption kinetics curves of propylene and propane in the adsorbent for propylene-propane separation provided in comparative example 1.
Fig. 3B is a graph comparing sorption kinetics curves of propylene and propane in the adsorbent for propylene-propane separation provided in comparative example 2.
Description of reference numerals:
1-air bath, 2-sapphire kettle, 3-magnetic stirring system, 4-high pressure blind kettle, 5-raw material gas storage bottle and pressure acquisition system 6.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present 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 in figure 1, the device comprises a raw material gas storage bottle 5, a high-pressure blind kettle 4 and a sapphire kettle 2 which are sequentially connected, 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 thermodynamic equilibrium experiments, kinetic separation experiments and experiments for separating propylene from propane in propylene-propane mixed gas are carried out, the method specifically comprises the following steps:
before the experiment begins, the sapphire kettle 2 is disassembled, the interior of the sapphire kettle and a stirrer are washed for three times by deionized water, and then are wiped dry, and a certain amount of prepared adsorbent is added; then, the sapphire kettle 2 is installed in the air bath 1 again, and the sapphire kettle 2 is vacuumized; vacuumizing the high-pressure blind kettle 4 and a pipeline system connected with the high-pressure blind kettle 4, introducing feed gas into the blind kettle to replace residual air, repeating the process for 3 times, and finally injecting the feed gas with certain pressure into the high-pressure blind kettle 4; opening a constant-temperature air bath to set the experiment temperature; when the temperature of the air bath 1 is stable and the pressure in the high-pressure blind kettle 4 is stable at a constant value, recording the corresponding pressure value p of the high-pressure blind kettle 41(ii) a And slowly opening a connecting valve between the high-pressure blind kettle 4 and the sapphire kettle 2, so that the gas in the high-pressure blind kettle 4 slowly flows into the sapphire kettle 2, and closing the connecting valve after a certain pressure is reached. The magnetic stirring system 3 is activated to accelerate the whole sorption process.
If a thermodynamic equilibrium experiment is carried out, when the pressure in the sapphire kettle 2 is unchanged and stable for 30min, an equilibrium state is reached, and the high-pressure blind kettle 4 (p) at the moment is respectively recorded2) And sapphire pot 2 (p)E) A medium pressure value; the steps are repeated until the equilibrium pressure reaches the experimental requirements.
If a kinetic separation experiment is carried out, the specified sorption time is set to t1When a predetermined adsorption time is reached, this is recordedThe pressure of the high-pressure blind kettle 4 is p2And the pressure of the sapphire pot 2 is pt1。
As in the gas mixture separation experiment, after the pressures of the sapphire pot 2 and the autoclave 4 were recorded when the specified adsorption time was reached, the gas mixture in the sapphire pot 2 was sampled and the gas mixture components were analyzed by HP7890 gas chromatography.
The total molar amount of gas (n) injected into the autoclave 4t) Calculated from the following formula:
wherein T is the temperature of the reaction system; p is a radical of1The initial pressure of the high-pressure blind kettle is obtained; p is a radical of2Balancing the pressure of the high-pressure blind kettle after injecting gas into the sapphire kettle; vtThe total effective volume of the high-pressure blind kettle and the connecting pipeline is shown; r is a gas constant; n istThe total molar amount of the gas injected into the high-pressure blind kettle 4; compression factor Z1、Z2Calculated by BWRS state equation (Benedict-Webb-Rubin-Starling).
The amount of the total material in the equilibrium gas phase n in the sapphire pot if a thermodynamic equilibrium experiment is carried outECalculated from the following formula:
in the formula, pEIs the equilibrium pressure in the sapphire kettle; zEIs a corresponding compression factor under the temperature and pressure in the sapphire kettle; vgIs the volume of the gas phase in the sapphire kettle; t is the temperature of the reaction system; r is a gas constant; n isEThe amount of total material in the gas phase in the sapphire pot was balanced.
If a kinetic separation experiment is carried out, t is reached at a defined sorption time1In the meantime, the amount n of the total gas phase in the sapphire pott1Calculated from the following formula:
in the formula, pt1To achieve a specified sorption time t1The pressure in the sapphire kettle; zt1Is the corresponding compression factor of the sapphire kettle under the temperature and pressure at the moment; vgIs the volume of the gas phase in the sapphire kettle; t is the temperature of the reaction system; r is a gas constant; n ist1To achieve a specified sorption time t1And (3) the total amount of gas phase substances in the sapphire kettle.
As performed in the mixed gas separation experiment, C adsorbed by the adsorbent3H6(n1) And C3H8(n2) Calculated by the following formula:
n1＝nt×z1-nt1×y1
n2＝nt×z2-nt1×y2
in the formula, z1Is C3H6Mole fraction in the feed gas; y is1Is the time of arrival of sorption C3H6The mole fraction in the mixed gas phase; z is a radical of2Is C3H8Mole fraction in the feed gas; y is2Is the time of arrival of sorption C3H8The mole fraction in the mixed gas phase; n istThe total molar amount of the gas injected into the high-pressure blind kettle 4; n ist1To achieve a specified sorption time t1The total amount of gas phase substances in the sapphire kettle; n is1C sorbed for adsorbent3H6Total gas moles of (a); n is2C sorbed for adsorbent3H8Total gas moles of (a).
C sorbed by adsorbents3H6Mole fraction (x)1) And C3H8Mole fraction (x)2) Calculated by the following formulas, respectively:
in the formula, n1C sorbed for adsorbent3H6Total gas moles of (a); n is2C sorbed for adsorbent3H8Total gas moles of (a); x is the number of1C sorbed for adsorbent3H6A mole fraction; x is the number of2C sorbed for adsorbent3H8Mole fraction.
C3H6Relative to C3H8Is calculated by the following formula:
in the formula, y1Is the time of arrival of sorption C3H6The mole fraction in the mixed gas phase; y is2Is the time of arrival of sorption C3H8The mole fraction in the mixed gas phase; x is the number of1C sorbed for adsorbent3H6A mole fraction; x is the number of2C sorbed for adsorbent3H8A mole fraction; beta is C3H6Relative to C3H8The separation factor of (1).
C3H6Solubility S ofVIs defined as:
VS＝h×π×r2
in the formula, VSCalculating the volume of the adsorbent according to 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 is1C sorbed for adsorbent3H6Total gas moles of (a); sVIs C3H6The solubility of (a).
The gas-liquid ratio φ is calculated by the following equation:
wherein phi is the gas-liquid ratio; n istThe total molar amount of the gas injected into the high-pressure blind kettle 4; vSThe 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 imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and ethylene glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 30 wt% of ZIF-8 zeolitic imidazolate framework and 70 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80 wt% of water and 20 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and ethylene glycol in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the ethylene glycol to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid as the adsorbent for propylene-propane separation.
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 a feed pressure of 150 KPa.
The kinetics curves of the adsorbents in this example for pure propylene and pure propane are shown in figure 2. As can be seen from fig. 2, the two gases are adsorbed in closer amounts in the adsorbent, but the rates of adsorption are very different: when the sorption time was 25min, the sorption amount of propene had reached 95% of the equilibrium sorption amount, whereas the sorption amount of propane was only 45% of the equilibrium sorption amount; when the sorption time reaches 40min, the propylene reaches gas-liquid equilibrium in the sorbent, and the propane needs 240min to reach the gas-liquid equilibrium state, so that the remarkable kinetic difference between the two provides feasibility for the sorbent to separate propylene-propane mixed gas kinetically.
Example 2
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and ethylene glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 10 wt% of ZIF-8 zeolitic imidazolate framework and 90 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80 wt% of water and 20 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and ethylene glycol in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the ethylene glycol to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid as the adsorbent for propylene-propane separation.
Example 3
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and ethylene glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 20 wt% of ZIF-8 zeolitic imidazolate framework and 80 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80 wt% of water and 20 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and ethylene glycol in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the ethylene glycol to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid as the adsorbent for propylene-propane separation.
Example 4
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and ethylene glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 30 wt% of ZIF-8 zeolitic imidazolate framework and 70 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 60 wt% of water and 40 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and ethylene glycol in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the ethylene glycol to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid as the adsorbent for propylene-propane separation.
Example 5
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and ethylene glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 30 wt% of ZIF-8 zeolitic imidazolate framework and 70 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 40 wt% of water and 60 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and ethylene glycol in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the ethylene glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the ethylene glycol to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid as the adsorbent for propylene-propane separation.
Example 6
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and isohexane glycol;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 30 wt% of ZIF-8 zeolitic imidazolate framework and 70 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80 wt% of water and 20 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and isohexane glycol in proportion, slowly adding ZIF-8 zeolite imidazolate framework material into a mixed solution of water and isohexane glycol, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of water and isohexane glycol to obtain ZIF-8 zeolite imidazolate framework material dispersion as the adsorbent for propylene-propane separation.
Example 7
This example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material dispersion liquid, and the dispersant used by the ZIF-8 zeolite imidazolate framework material dispersion liquid is a mixture of water and 1, 3-dimethyl propylene urea;
the ZIF-8 zeolitic imidazolate framework dispersion comprises 30 wt% of ZIF-8 zeolitic imidazolate framework and 70 wt% of dispersant, based on 100% of the total mass of the adsorbent for propylene-propane separation; the dispersed phase comprises 80 wt% of water and 20 wt% of a hydrophilic solvent based on 100% of the total mass of the dispersing agent;
the preparation method specifically comprises the following steps:
uniformly mixing water and 1, 3-dimethyl propylene urea in proportion, slowly adding the ZIF-8 zeolite imidazolate framework material into a mixed solution of the water and the 1, 3-dimethyl propylene urea, and fully and uniformly stirring until ZIF-8 is uniformly dispersed in the mixed solution of the water and the 1, 3-dimethyl propylene urea to obtain a ZIF-8 zeolite imidazolate framework material dispersion liquid serving as the propylene-propane separation adsorbent.
Comparative example 1
The comparative example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material.
At the temperature of 20 ℃ and the inlet pressure of 380KPa, based on the adsorbent provided by the comparative example, thermodynamic equilibrium experiments and kinetic separation experiments of pure propylene and pure propane are carried out.
The kinetics of the adsorbent in this comparative example were plotted for pure propylene and pure propane, with the results shown in FIG. 3A. As can be seen from fig. 3A, the adsorption behavior of the two gases on the adsorbent is very similar, and both gases achieve gas-solid equilibrium around 20min, and exhibit very fast adsorption rate (0-3min) in the early stage of adsorption, even though the adsorption capacities are relatively close, and the two gases simultaneously exhibit similar kinetic properties.
Comparative example 2
The comparative example provides an adsorbent for propylene propane separation
The adsorbent is ZIF-8 zeolite imidazolate framework material.
Based on the adsorbent provided in the comparative example, a thermodynamic equilibrium experiment and a kinetic separation experiment of pure propylene and pure propane were performed at a temperature of 20 ℃ and a feed pressure of 150 KPa.
The kinetics curves of the adsorbent in this comparative example for pure propylene and pure propane are shown in fig. 3B. As can be seen from FIG. 3B, the adsorption behavior of the two gases on the adsorbent is very similar, and the two gases have relatively similar adsorption capacities and simultaneously show similar dynamic performance, both reach gas-solid equilibrium in about 10min, and simultaneously show very fast adsorption rate (0-2min) in the early stage of adsorption.
As can be seen by comparing FIG. 2 with FIGS. 3A and 3B, the pure solid ZIF-8 zeolite imidazolate framework material does not effectively separate the propylene-propane mixture, either thermodynamically or kinetically. The solid ZIF-8 zeolite imidazolate framework material is dispersed in the mixed solution of liquid phase water and ethylene glycol by the adsorbent provided in the embodiment 1, the mixed solution of water and ethylene glycol can form a layer of dense semipermeable membrane on the surface of the ZIF-8 zeolite imidazolate framework material, the existence of the semipermeable membrane remarkably reduces the adsorption rate of the ZIF-8 zeolite imidazolate framework material in the liquid phase to propylene propane molecules, and meanwhile, due to the different properties of gas molecules, the adsorption rate of the propane molecules is greatly reduced, and the degree of reduction of the adsorption rate of the propylene molecules is small. Therefore, the adsorbent provided by the embodiment 1 can be used for dynamically separating 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
This example provides a propylene-propane separation method, which is performed in the manner adopted in the above experiment for separating propylene from propane in a propylene-propane mixture.
In this example, propylene-propane separation was performed at different adsorption times using the adsorbent for propylene-propane separation provided in example 1, and the results are shown in table 1. The experimental temperature is fixed at 293.15K, the initial gas-liquid ratio is fixed at about 19, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixed gas) is 1: 1.
From table 1 it can be seen that with increasing sorption time the propylene solubility increases and then stabilizes, the propylene concentration in the gas phase decreases and then increases and the separation factor increases and then decreases. It can be seen that the time interval of 20-30min is the optimum time for the kinetic separation of propylene and propane, and in this time region, the separation factor reaches about 8.6, and the propylene concentration in the gas phase is reduced to about 20 mol%. Generally, the adsorption separation effect is realized when beta is more than 2.0, the industrial application value is realized when beta is more than 3.0, and the separation factor of the liquid absorption/adsorption agent on propylene/propane reaches 8.6, so that the liquid absorption/adsorption agent has a wider propylene-propane separation application value.
TABLE 1
Example 9
This example provides a propylene-propane separation method, which is performed in the manner adopted in the above experiment for separating propylene from propane in a propylene-propane mixture.
In this example, propylene-propane separation was performed on a propylene-propane mixed gas having different compositions of propylene and propane by using the adsorbent for propylene-propane separation provided in example 1, and the results are shown in table 2. The experimental temperature is fixed at 273.15K, the initial gas-liquid ratio is fixed at about 19, and the adsorption time is fixed at 20 min.
TABLE 2
| z1(mol％) | Φ | Pt1/(bar) | SV(mol/L) | y1(mol％) | x1(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 |
It can be seen from table 2 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 is better for raw material gas with low propylene concentration.
In industrial application, multi-stage separation is often required for separating propylene and propane, in other words, effective separation of propylene and propane mixed gas composed of different propylene and propane is required, and table 2 shows that the adsorbent provided in example 1 has good separation effect on propylene and propane mixed gas composed of different propylene and propane, so that the adsorbent for separating propylene and propane provided by the invention has an industrial multi-stage separation application prospect.
Example 10
This example provides a propylene-propane separation method, which is performed in the manner adopted in the above experiment for separating propylene from propane in a propylene-propane mixture.
In this example, propylene-propane separation was performed on a propylene-propane mixed gas composed of propylene and propane by using the adsorbents for propylene-propane separation provided in example 1, example 2, and example 3, and the results are shown in table 3. The experimental temperature is fixed at 293.15K, the initial gas-liquid ratio is fixed at about 19, the adsorption time is fixed at 20min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixed gas) is 1: 1.
As can be seen from Table 3, the adsorbents with different solid contents have certain separation effect on propylene-propane mixed gas, the separation factor is increased along with the increase of the solid content, and the separation effect is obviously improved, so that the ZIF-8 plays a leading role in the adsorbents.
TABLE 3
| Source of adsorbent | Solid content | Φ | Pt1/(bar) | SV(mol/L) | y1(mol％) | x1(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
This example provides a propylene-propane separation method, which is performed in the manner adopted in the above experiment for separating propylene from propane in a propylene-propane mixture.
In this example, propylene-propane separation was performed on a propylene-propane mixed gas composed of propylene and propane by using the adsorbents for propylene-propane separation provided in examples 1, 4 and 5, and the results are shown in table 4. The experimental temperature is fixed at 293.15K, the initial gas-liquid ratio is fixed at about 19, the adsorption time is fixed at 15min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixed gas) is 1: 1.
As can be seen from Table 4, the adsorbents composed of different liquid phases can perform a certain separation effect on propylene-propane mixed gas, and the higher the content of ethylene glycol in the liquid phase is, the lower the separation factor is, and the poorer the separation effect is. The increase of the content of the ethylene glycol leads to the increase of the viscosity of the adsorbent, the mass transfer rate is lowered, the difference of the sorption rates of the two gases is reduced, and the kinetic separation effect is deteriorated. Therefore, the effect of controlling the content of the ethylene glycol in the liquid phase to be about 20 percent is optimal.
TABLE 4
| Source of adsorbent | Ethylene glycol content | Φ | Pt1/(bar) | SV(mol/L) | y1(mol％) | x1(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
This example provides a propylene-propane separation method, which is performed in the manner adopted in the above experiment for separating propylene from propane in a propylene-propane mixture.
In this example, propylene-propane separation was performed on a propylene-propane mixed gas composed of propylene and propane by using the adsorbents for propylene-propane separation provided in examples 1, 6, and 7, and the results are shown in table 5. The experimental temperature is fixed at 293.15K, the initial gas-liquid ratio is fixed at about 19, the adsorption time is fixed at 20min, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixed gas) is 1: 1.
As can be seen from table 5, ethylene glycol, isohexide, 1, 3-dimethylpropylene urea and water are used in combination as a liquid phase solvent, and all have good separation effects on propylene-propane mixed gas, wherein the separation effect brought by the 1, 3-dimethylpropylene urea as the liquid phase solvent is optimal, and the influence of ethylene glycol and isohexide as the solvent on the separation effect is small.
TABLE 5
Example 13
This example was conducted to verify the regeneration performance of the adsorbent for propylene-propane separation 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, an experiment for separating propylene from propane in a propylene-propane mixed gas was performed based on the adsorbent for propylene-propane separation provided in example 1, and then the adsorbent after the experiment was desorbed and the experiment for separating propylene from propane in a propylene-propane mixed gas under the same conditions was repeated 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 to propane in the raw material gas-propylene-propane mixed gas is 1:1, the desorption condition is 298.15K, and the vacuum pumping is carried out for 1h, and the results are shown in Table 6.
TABLE 6
| Number of repetitions | Φ | Pt1/(bar) | SV(mol/L) | y1(mol％) | x1(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 always maintained around 0.33mol/L with the accumulation of the number of experiments, the propylene concentration in the gas phase could be reduced to about 18 mol%, and the separation factor was always maintained between 11 and 12, which demonstrates that the adsorbent for separating propylene from propane provided in example 1 has good regeneration performance, and at the same time, the regeneration conditions are mild, and can be repeatedly used for separating propylene from propane in the propylene-propane mixed gas.
Comparative example 3
The comparative example provides a propylene-propane separation method, which is carried out in the manner adopted in the separation experiment of propylene and propane in the propylene-propane mixed gas.
This comparative example used the adsorbent for propylene-propane separation provided in comparative example 1 to perform propylene-propane separation at different sorption times, and the results are shown in table 7. The experimental temperature is fixed at 293.15K, the initial gas-liquid ratio is fixed at about 19, and the molar concentration ratio of propylene to propane in the feed gas (propylene-propane mixed gas) is 1: 1. When the reaction time reaches 40min, the gas-solid two phases reach thermodynamic equilibrium and belong to thermodynamic separation; when the reaction time is 5min, the kinetic separation is carried out. As can be seen from table 7, the adsorbent exhibited some propane selectivity at this time, but the separation factor was low, only around 1.25. The experiment on propylene-propane separation by using pure ZIF-8 shows that no matter how long the adsorption time is, the separation factor is very low, and the separation effect is poor.
TABLE 7
| t(min) | Φ | Pt1/(bar) | SV(mol/L) | y1(mol％) | x1(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 principle and the implementation mode of the invention are explained by applying specific embodiments in the invention, and the description of the embodiments is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. An adsorbent for separating propylene and propane is a dispersion liquid and comprises a dispersion phase and a dispersing agent; wherein the content of the first and second substances,
the dispersed phase comprises a zeolitic imidazolate framework material;
the dispersant includes water and a hydrophilic solvent.
2. The adsorbent according to claim 1, wherein the adsorbent for propylene propane separation comprises 10% to 30% of an imidazolate framework material and 70% to 90% of a dispersant, based on 100% of the total mass of the adsorbent for propylene propane separation.
3. The adsorbent according to claim 1, wherein 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.
4. The adsorbent of any one of claims 1-3, wherein the zeolitic imidazolate framework is a ZIF-8 zeolitic imidazolate framework.
5. The adsorbent according to any one of claims 1 to 3, wherein the hydrophilic solvent is one or a combination of two or more selected from the group consisting of ethylene glycol, isohexanol, and 1, 3-dimethylpropylene urea.
6. A process for producing an adsorbent for propylene propane separation as claimed in any one of claims 1 to 5, wherein the process comprises:
mixing water and a hydrophilic solvent, and then adding a zeolite imidazolate framework material to obtain a dispersion liquid of the zeolite imidazolate framework material as the propylene-propane separation adsorbent.
7. A propylene-propane separation method, wherein the method uses the adsorbent for propylene-propane separation according to any one of claims 1 to 5 to separate propylene from propane.
8. The propylene propane separation process of claim 7, wherein the propylene propane separation is conducted at 0 ℃ to 40 ℃.
9. The propylene propane separation process according to claim 7, wherein the sorption time for propylene propane separation is 5min to 240 min.
10. The propylene propane separation process according to claim 7, wherein,
in the propylene-propane mixed gas, the content of propylene is 6-85 mol% based on the total molar weight of propylene-propane as 100%;
the volume ratio of the propylene-propane mixed gas to the propylene-propane separating adsorbent is 13-21.
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| CN110368902A (en) * | 2018-04-12 | 2019-10-25 | 中国石油大学(北京) | A kind of guard method of zeolitic imidazolate framework material |
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| CN110368902A (en) * | 2018-04-12 | 2019-10-25 | 中国石油大学(北京) | A kind of guard method of zeolitic imidazolate framework material |
| CN110639474A (en) * | 2019-09-28 | 2020-01-03 | 华南理工大学 | Adsorbent for separating propylene and propane and preparation method thereof |
| KR20210061586A (en) * | 2019-11-20 | 2021-05-28 | 부산대학교 산학협력단 | Cesium adsorbent and preparation method thereof |
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