CN114288810B - Application of microporous carbon material in adsorption separation of olefin and alkane - Google Patents
Application of microporous carbon material in adsorption separation of olefin and alkane Download PDFInfo
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Abstract
The application relates to an application of a microporous carbon material in adsorption separation of olefin and alkane, wherein the preparation method of the microporous carbon material comprises the following steps: s1: carrying out hydrothermal reaction on the sucrose solution to obtain coke; s2: and carrying out pore-forming treatment on the coke to obtain the microporous carbon material. The microporous carbon material adopted by the method has the characteristics of good stability, developed pore structure and large specific surface area, and has higher selectivity when being used for dynamically adsorbing and separating olefin and alkane.
Description
Technical Field
The application relates to an application of a microporous carbon material in adsorption separation of olefin and alkane.
Technical Field
Ethylene and propylene are two important organic chemical raw materials with the largest global yield and dosage, and the productivity of the ethylene and the propylene marks the development level of the national petrochemical industry. High purity olefin products are widely used in the production of polymers. Olefins are mainly produced by cracking naphtha, a large amount of alkanes with the same carbon number also exist in the production process, however, the structures of ethylene and ethane, propylene and propane are highly similar, the boiling points are similar, and how to remove corresponding alkane compounds in olefin products becomes a big problem restricting the production process of polymerization-grade olefins.
At present, the industry still depends on cryogenic rectification to separate ethylene, ethane and propylene and propane, however, the adsorption separation technology has the defects of huge energy consumption, high equipment requirement, energy conservation, high efficiency and low equipment investment, and is widely favored in recent years. The common adsorption separation mechanisms mainly comprise three types of molecular sieve separation, thermodynamic equilibrium separation and kinetic separation. Bao et al have implemented molecular sieve separations of ethylene ethane using gallic acid salt metal organic framework materials (angelw. Chem. Int. Ed.,2018,57,16020-16025.). Cadiau et al have invented a pillared metal organic framework material NbOFFIVE-1-Ni for the molecular sieving separation of propylene propane (Science, 2016,353 (6295): 137.). Although their separation selectivity is high, their adsorption capacity is low. Bao et al use a metal organic framework material Mg-MOF-74 with open metal sites to achieve propylene propane separation by force differential (Langmuir, 2011,27,22,13554-13562.), but this material is poor in water stability and can form strong forces with carbon-carbon double bonds in olefins, resulting in high energy consumption for regeneration. The dynamic separation is mainly based on the gas diffusion rate difference to realize the high-efficiency separation of the mixed gas, the acting force is moderate, the regeneration energy consumption is low, and the method has industrial application prospect.
Microporous carbon materials have been extensively studied for their good stability, developed pore structure, and large specific surface area. However, in the general preparation process of the carbon material, an organic pore regulator needs to be added for activating and pore-forming treatment, so that environmental pollution is caused, the aperture of the obtained carbon material is wide, the strict requirement of gas dynamic separation with similar structure is difficult to meet, and the improvement of the selectivity of adsorption separation is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides the application of the microporous carbon material in the kinetic adsorption separation of olefin and alkane, the microporous carbon material adopted by the application has good stability, developed pore structure and large specific surface area, and the application of the microporous carbon material in the kinetic adsorption separation of olefin and alkane has high adsorption separation selectivity.
The application provides an application of a microporous carbon material in adsorption separation of olefin and alkane, wherein the preparation method of the microporous carbon material comprises the following steps:
s1: carrying out hydrothermal reaction on the sucrose solution to obtain coke;
s2: and carrying out pore-forming treatment on the coke to obtain the microporous carbon material.
According to some embodiments of the present application, in step S1, the sucrose solution is an aqueous solution of sucrose. According to some embodiments of the present application, the sucrose solution has a concentration of 0.5mol/L to 2.0mol/L, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, and any value therebetween. According to a preferred embodiment of the present application, it is preferably from 0.5mol/L to 1.0mol/L.
According to some embodiments of the present application, in step S1, the temperature of the hydrothermal reaction is 150 ℃ to 250 ℃, and may be, for example, 150 ℃,160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ and any value therebetween. According to a preferred embodiment of the present application, in step S1, the temperature of the hydrothermal reaction is 180 ℃ to 200 ℃.
According to some embodiments of the present application, the temperature of the hydrothermal reaction is achieved by temperature programming. According to some embodiments of the present application, the temperature ramp rate of the programmed temperature is 2 ℃/min to 5 ℃/min, and can be, for example, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, and any value therebetween. According to a preferred embodiment of the present application, the temperature rise rate of the temperature programming is 2.5 ℃/min to 3.5 ℃/min.
According to some embodiments of the present application, the hydrothermal reaction time is 3h to 10h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and any value therebetween. According to some preferred embodiments of the present application, the hydrothermal reaction time is 5h to 10h.
According to some embodiments of the present application, in step S2, the pore-forming treatment is a pyrolysis pore-forming. According to some embodiments of the present application, the pyrolytical pore formation temperature is in the range of 400 ℃ to 800 ℃, and may be, for example, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, and any value therebetween. According to a preferred embodiment of the present application, the temperature of the pyrolitic pore forming is 600-800 ℃. According to some embodiments of the present application, the pyrolytically induced pore formation temperature is 650 ℃ or 750 ℃.
According to some embodiments of the present application, in the pore-forming process, the pyrolysis pore-forming temperature is directly cooled after reaching the target temperature in the pore-forming process in step S2.
According to some embodiments of the present application, the temperature of the pyrolytically-induced pore formation is achieved by temperature programming. According to some embodiments of the present application, the temperature ramp rate of the temperature program is from 1 ℃/min to 10 ℃/min. According to a preferred embodiment of the present application, the temperature of the pyrolytic pore-forming is achieved by stepwise temperature programming. According to some embodiments of the present application, the temperature of the pyrolytic pore-forming is achieved by first raising the temperature at a rate of 1 ℃/min to 3 ℃/min, and then raising the temperature at a rate of 5 ℃/min to 8 ℃/min.
According to some embodiments of the present application, in step S2, the pore-forming treatment is performed under the protection of an inert gas. According to some embodiments of the present application, the inert gas is one of nitrogen, argon or helium.
According to some embodiments of the present application, the inert gas has a gas flow rate of 10mL/min to 500mL/min, for example, 10mL/min, 50mL/min, 100mL/min, 150mL/min, 200mL/min, 300mL/min, 400mL/min, 500mL/min, and any value therebetween. According to a preferred embodiment of the present application, the inert gas has a gas flow rate of 25mL/min to 100mL/min.
According to some embodiments of the present application, the method further comprises grinding the tablet after drying the coke before step S2.
According to some embodiments of the present application, a method of making a microporous carbon material comprises:
step (1), preparing carbon coke by hydrothermal carbonization reaction:
weighing a certain amount of sucrose, adding the sucrose into deionized water to prepare a sucrose solution with the concentration of 0.5mol/L-2.0mol/L, immediately transferring the sucrose solution into a hydrothermal reaction kettle with the filling amount of 50% -90% of the total volume of the reaction kettle, then putting the reaction kettle into a temperature programming oven, raising the temperature to 150 ℃ -250 ℃ through a program, and reacting for 5h-10h at a high temperature to obtain homogeneous charcoal coke.
Step (2), temperature programming, pyrolysis and pore forming:
drying the carbon coke prepared in the step (1) without washing, grinding and tabletting, placing the carbon coke in a tubular furnace, adopting inert gas for protection, setting the gas flow rate to be 25mL/min-500mL/min, adopting staged temperature programming, firstly heating at the speed of 1 ℃/min-3 ℃/min, then continuously heating at the speed of 5 ℃/min-8 ℃/min, raising the temperature to 400 ℃ -1000 ℃, directly cooling after reaching the target temperature, and obtaining the microporous carbon material with uniform aperture, wherein the aperture of micropores of the microporous carbon material is regulated and controlled by the gas flow rate, pyrolysis temperature, heating rate and the like.
According to other embodiments of the present application, the microporous carbon material is prepared by: preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the rate of 3 ℃/min for reaction for 5h, then directly drying, grinding and tabletting the obtained carbon coke, transferring the carbon coke into a tubular furnace, raising the temperature to 500 ℃ at the rate of 1 ℃/min in an inert gas atmosphere, raising the temperature to 650-750 ℃ at the rate of 5 ℃/min for high-temperature activation (pyrolysis pore-forming), and obtaining the specific surface area of 400-600m 2 A microporosity of 100% and an effective micropore diameter of
The microporous carbon material of (1).
According to other embodiments of the present application, the microporous carbon material is prepared by: preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, increasing the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, increasing the temperature to 500 ℃ at the heating rate of 1 ℃/min in an inert gas atmosphere, increasing the temperature to 650 ℃ at the heating rate of 5 ℃/min for high-temperature activation (pyrolysis pore-forming) to obtain a specific surface area of 466m 2 The microporosity is 100 percentEffective micropore diameter of
The microporous carbon material of (1).
According to other embodiments of the present application, the microporous carbon material is prepared by: preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the rate of 3 ℃/min for reaction for 5h, then directly drying, grinding and tabletting the obtained carbon coke, transferring the carbon coke into a tubular furnace, raising the temperature to 500 ℃ at the rate of 1 ℃/min in an inert gas atmosphere, raising the temperature to 750 ℃ at the rate of 5 ℃/min for high-temperature activation (pyrolysis pore-forming), and obtaining the specific surface area of 536m 2 A microporosity of 100% and an effective micropore diameter of
The microporous carbon material of (3).
The preparation method has the advantages that the sucrose solution is adopted to carry out hydrothermal carbonization reaction to prepare the carbon coke, and then the temperature programming pyrolysis pore-forming is carried out to prepare the microporous carbon material.
According to some embodiments of the present application, the microporous carbon material has a specific surface area of 300m 2 /g-800m 2 A/g, for example, of 300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g、500m 2 /g、550m 2 /g、600m 2 /g、650m 2 /g、700m 2 /g、750m 2 /g、800m 2 G and any value in between. According to a preferred embodiment of the present application, the microporous carbon material has a specific surface area of 400m 2 /g-600m 2 (iv) g. According to a preferred embodiment of the present application, the microporous carbon material has a specific surface area of 466m 2 In g or 536m 2 /g。
According to some embodiments of the present application, the microporous carbon material has a microporosity of 80% to 100%, for example, 80%, 85%, 90%, 95%, 100%, and any value therebetween. According to a preferred embodiment of the present application, the microporous carbon material has a microporosity of 95% to 100%. According to some embodiments of the present application, the microporous carbon material has a microporosity of 100%. In the present application, microporosity refers to the proportion of micropore volume to total pore volume.
According to some embodiments of the present application, the microporous carbon material has an effective micropore pore size of
For example, can be->
And any value in between. According to a preferred embodiment of the present application, the microporous carbon material has an effective micropore pore size->
According to a preferred embodiment of the present application, the microporous carbon material has an effective micropore pore size +>
Or>
In the present application, the average value of the molecular size of the largest dimension that can be adsorbed by the microporous carbon material and the molecular size of the smallest dimension that cannot be adsorbed is referred to as the effective micropore diameter of the microporous carbon material, using gas molecules having different kinetic diameters or collision diameters as probes.
According to some embodiments of the present application, the shape of the microporous carbon material includes at least one of spheres, pillars, particles, or membranes.
The microporous carbon material for kinetic adsorption and separation of olefin and alkane has the characteristics of narrow and uniform pore size distribution, large specific surface area and high selectivity, and can be used for pressure swing adsorption of olefin and alkane.
According to some embodiments of the present application, the alkane comprises a C2-C6 alkane. According to some embodiments of the present application, the alkane comprises ethane and/or propane.
According to some embodiments of the present application, the olefins include C2-C6 olefins. According to some embodiments of the present application, the olefin comprises ethylene and/or propylene.
According to some embodiments of the present application, the temperature of the adsorptive separation is between-5 ℃ and 50 ℃, and may be, for example, -5 ℃, 0 ℃,5 ℃, 15 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃ and any value in between.
According to some embodiments of the present application, in the adsorptive separation, the total pressure of the mixed gas comprising the alkene and the alkane is from 100kPa to 1000kPa, and may be, for example, 100kPa, 200kPa, 400kPa, 600kPa, 800kPa, 1000kPa, and any value therebetween.
According to some embodiments of the present application, the adsorptive separation is a kinetic adsorptive separation.
Compared with the prior art, the invention has the following advantages:
the sucrose used for preparing the microporous carbon material has wide source and low price. The preparation method of the microporous carbon material is simple and green, and a chemical pore-forming agent is not required to be added. The microporous carbon material has stable structure and performance, has higher adsorption capacity on olefin, has higher dynamic adsorption selectivity on olefin and alkane, and still keeps the original effect on the adsorption performance after repeated adsorption-regeneration. The performance in the aspect of kinetic adsorption separation of olefin and alkane is far better than that of most solid adsorbents.
Drawings
FIG. 1 is an adsorption isotherm of propylene and propane by the microporous carbon material prepared according to example 1 of the present application.
FIG. 2 is a graph of the adsorption kinetics of a microporous carbon material prepared according to example 1 of the present application for propylene and propane.
FIG. 3 is a fixed bed breakthrough curve for propylene and propane mixed gas for the microporous carbon material prepared according to example 1 of the present application.
FIG. 4 is an adsorption isotherm of ethylene and ethane for a microporous carbon material prepared according to example 2 of the present application.
FIG. 5 is a graph of the adsorption kinetics for ethylene and ethane for a microporous carbon material prepared according to example 2 of the present application.
FIG. 6 is a fixed bed breakthrough curve for ethylene and ethane mixtures for microporous carbon material prepared according to example 2 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, the reagents and apparatus used are not indicated by the manufacturer, but are all conventional products commercially available.
Example 1
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the rate of 1 ℃/min, raising the temperature to 650 ℃ at the rate of 5 ℃/min for high-temperature activation and pore-forming in the nitrogen atmosphere, and directly cooling after reaching the target temperature to obtain the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 466m 2 In g, effective micropore diameter of
In order to test the adsorption performance of the microporous carbon material prepared in this example, a single-component adsorption experiment of propylene and propane was performed using the above microporous carbon material as an adsorbent. The resulting microporous carbon material was degassed at 150 ℃ for 24 hours, followed by a gas adsorption experiment. 100mg of the adsorbent was taken and the adsorption temperature was set at 25 ℃. As a result of the test, as shown in FIG. 1, at 25 ℃ and 1bar, the adsorption amount of propylene reached 2.31mmol/g, while that of propane reached 1.91mmol/g. The adsorption selectivity of the adsorbent to propylene propane is 1.2 calculated by a Henry coefficient.
In order to test the kinetic adsorption performance of the microporous carbon material prepared in this example on propylene and propane, a single-component kinetic adsorption experiment of propylene and propane was performed using the above microporous carbon material as an adsorbent. 100mg of the adsorbent was taken and the adsorption temperature was set at 25 ℃. As a result of the test, as shown in FIG. 2, at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium at 15 minutes, whereas propane reached the adsorption equilibrium at 2200 minutes. The kinetic adsorption selectivity of the adsorbent to propylene propane is up to 211 calculated by the diffusion coefficient.
In order to test the practical effect of the microporous carbon material prepared in this example on the separation of a mixture of propylene and propane, a breakthrough experiment of a mixture of propylene and propane was performed using the above-synthesized microporous carbon material as an adsorbent. In the present example, the adsorption separation was carried out on a propylene-propane mixed gas at a volume ratio of 50, a breakthrough temperature of 25 ℃ and a pressure of 0.1MPa. As a result of the test, as shown in FIG. 3, when the volume ratio of propylene to propane was 50 and the flow rate of the mixed gas was 1.6mL/min, the breakthrough of propane started at the beginning, whereas the breakthrough of propylene started at 45 minutes (per g of the adsorbent) and the dynamic adsorption amount of propylene was 1.90mmol/g.
Example 2
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 750 ℃ at the heating rate of 5 ℃/min for high-temperature activation and pore-forming in a nitrogen atmosphere. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 536m 2 Effective in/gPore diameter of the micropores
In order to test the adsorption performance of the microporous carbon material prepared in this example, a single-component adsorption experiment of ethylene and ethane was performed using the above microporous carbon material as an adsorbent. The resulting microporous carbon material was degassed at 150 ℃ for 24 hours, followed by a gas adsorption experiment. 100mg of the adsorbent was taken and the adsorption temperature was set at 25 ℃. As a result of the test, as shown in FIG. 4, at 25 ℃ and 1bar, the adsorption amount of ethylene reached 2.51mmol/g, whereas the adsorption amount of ethane was only 2.27mmol/g. The adsorption selectivity of the adsorbent to ethylene ethane is 1.41 calculated by a Henry coefficient.
In order to test the kinetic adsorption performance of the microporous carbon material prepared in this example on ethylene and ethane, a single-component kinetic adsorption experiment of ethylene and ethane was performed using the above microporous carbon material as an adsorbent. 50mg of the adsorbent was taken and the adsorption temperature was set at 25 ℃. The results are shown in FIG. 5, where ethylene reached the adsorption equilibrium at 25 ℃ and 100kPa in 20 minutes, while ethane reached the adsorption equilibrium only at 800 minutes. The dynamic adsorption selectivity of the adsorbent to ethylene ethane reaches 79.4 calculated by a diffusion coefficient.
In order to test the practical effect of the microporous carbon material prepared in this example on the separation of a mixed gas of ethylene and ethane, a breakthrough experiment of a mixed gas of ethylene and ethane was performed using the above-synthesized microporous carbon material as an adsorbent. In this example, the adsorption separation was carried out using a mixed gas of ethylene and ethane at a volume ratio of 50, a breakthrough temperature of 25 ℃ and a pressure of 0.1MPa. As a result of the test, as shown in FIG. 6, when the volume ratio of ethylene to ethane was 50 and the flow rate of the mixed gas was 1.4mL/min, the breakthrough of ethane started at the beginning, whereas the breakthrough of ethylene started at 30 minutes (per g of the adsorbent) and the dynamic adsorption amount of ethylene was 1.38mmol/g.
Example 3
Preparing 0.5mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 650 ℃ at the heating rate of 5 ℃/min for high-temperature activation and pore-forming in a nitrogen atmosphere. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 495m 2 Per g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was tested that the adsorption of propene reached 2.36mmol/g and the adsorption of propane 0.06mmol/g at 25 ℃ and 1 bar. The material can realize propylene-propane screening separation.
The single-component kinetic adsorption experiment of propylene and propane was carried out in the same manner as in example 1. Tests have shown that at 25 ℃ and 100kPa, propylene reaches the adsorption equilibrium only after 40 minutes, and that it is difficult to reach the kinetic adsorption equilibrium since propane hardly adsorbs.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. The test shows that the penetration of propane starts at the beginning and that the penetration of propylene starts at 12 minutes (per g of adsorbent) due to the slower diffusion of propylene, with a dynamic adsorption of propylene of only 0.55mmol/g.
Example 4
The microporous carbon material prepared in this example was the same as in example 3.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. The adsorption of ethylene at 25 ℃ and 1bar was found to be 2.28mmol/g and the adsorption of ethane at 1.79mmol/g. The adsorption selectivity of the adsorbent to ethylene ethane is 1.28 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 14 minutes, whereas ethane reached the adsorption equilibrium at 140 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane is calculated by a diffusion coefficient and reaches 18.7.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. The tests show that ethane breakthrough starts at 4 minutes, ethylene breakthrough starts at 20 minutes (per g of adsorbent), and the dynamic adsorption of propylene is only 1.14mmol/g.
Example 5
Preparing 1.0mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 650 ℃ at the heating rate of 5 ℃/min for high-temperature activation and pore-forming in a nitrogen atmosphere. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 442m 2 In g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was tested that the adsorption of propylene reached 2.15mmol/g and that of propane 1.54mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to propylene propane is 1.08 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of propylene and propane were performed in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium in 7 minutes and propane reached the adsorption equilibrium in 40 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane is up to 61 through the calculation of diffusion coefficient.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. It was tested that the breakthrough of propane started at 10 minutes, whereas the breakthrough of propylene started at 25 minutes (per g of adsorbent), and the dynamic adsorption of propylene was 1.04mmol/g.
Example 6
The microporous carbon material prepared in this example was the same as in example 5.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption of ethylene reached 2.15mmol/g and the adsorption of ethane 1.54mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene ethane is 1.08 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 5 minutes and ethane reached the adsorption equilibrium at 7 minutes. The dynamic adsorption selectivity of the adsorbent to ethylene ethane is 1.9 calculated by a diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. It was tested that ethane started breakthrough at 10 minutes, whereas ethylene started breakthrough at 12 minutes (per g of adsorbent), with a dynamic adsorption of ethylene of 0.91mmol/g.
Example 7
Preparing a 2.0mol/L sucrose solution, filling the sucrose solution into 90% of a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 650 ℃ at the heating rate of 5 ℃/min for high-temperature activation and pore-forming in a nitrogen atmosphere. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 408m 2 In g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was tested that the adsorption of propylene reached 1.76mmol/g and that of propane 1.49mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to propylene propane is 1.05 calculated by a Henry coefficient.
The single-component kinetic adsorption experiment of propylene and propane was carried out in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium in 9 minutes, whereas propane reached the adsorption equilibrium in 38 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane is 49 calculated by a diffusion coefficient.
The same procedure as in example 1 was used to conduct a breakthrough test of a mixed gas of propylene and propane. The tests show that the breakthrough of propane starts at 9 minutes, the breakthrough of propylene starts at 20 minutes (in terms of per g of adsorbent), and the dynamic adsorption amount of propylene is 0.92mmol/g.
Example 8
The microporous carbon material prepared in this example was the same as in example 7.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption of ethylene reached 1.61mmol/g and the adsorption of ethane 1.51mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene and ethane is 1.02 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 5 minutes and ethane reached the adsorption equilibrium at 6 minutes. The dynamic adsorption selectivity of the adsorbent to ethylene ethane reaches 1.3 through the calculation of a diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. The test showed that the breakthrough of ethane started at 10 minutes and the breakthrough of ethylene started at 11 minutes (per g of adsorbent) and that the dynamic adsorption of ethylene was 0.63mmol/g.
Example 9
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 600 ℃ at the heating rate of 5 ℃/min for high-temperature activation pore-forming in a nitrogen gas atmosphere. And after the target temperature is reached, directly cooling to prepare the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 436m 2 In g, effective micropore diameter of
Single component adsorption experiments of propylene and propane were performed in the same manner as in example 1. It was tested that the adsorption of propylene reached 2.11mmol/g and that of propane 1.52mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to propylene propane is 1.1 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of propylene and propane were performed in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium in 8 minutes, whereas propane reached the adsorption equilibrium in 40 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane reaches 58 calculated by a diffusion coefficient.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. It was tested that the breakthrough of propane started at 9 minutes, whereas the breakthrough of propylene started at 23 minutes (per g of adsorbent), and the dynamic adsorption of propylene was 1.01mmol/g.
Example 10
The microporous carbon material prepared in this example was the same as in example 9.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption of ethylene reached 2.01mmol/g and the adsorption of ethane 1.78mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene ethane is 1.01 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 5 minutes and ethane reached the adsorption equilibrium at 6 minutes. The kinetic adsorption selectivity of the adsorbent to ethylene ethane is 1.2 calculated by diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. The dynamic adsorption of ethylene was tested to be 0.78mmol/g, with ethane breakthrough beginning at 11 minutes and ethylene breakthrough beginning at 13 minutes (per g of adsorbent).
Example 11
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and raising the temperature to 1000 ℃ at the heating rate of 5 ℃/min for high-temperature activation pore-forming in a nitrogen gas atmosphere. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 624m 2 In g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was found that the adsorption of propylene was 0.06mmol/g and the adsorption of propane was 0.04mmol/g at 25 ℃ and 1 bar. The adsorbent has little separation selectivity to propylene propane.
Single component kinetic adsorption experiments of propylene and propane were performed in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, it was difficult to reach equilibrium of adsorption kinetics, since propylene and propane are not substantially adsorbed.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. The material has no practical separation performance on propylene and propane.
Example 12
The microporous carbon material prepared in this example was the same as in example 11.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption capacity of ethylene was 2.38mmol/g and that of ethane was 2.19mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene ethane is 1.03 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 12 minutes and ethane reached the adsorption equilibrium at 18 minutes. The kinetic adsorption selectivity of the adsorbent to ethylene ethane is 1.6 calculated by a diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. The tests show that ethane breakthrough occurred over 12 minutes, whereas ethylene breakthrough began over 14 minutes (per g of adsorbent), with a dynamic adsorption of 1.01mmol/g ethylene.
Example 13
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5 hours, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min in the nitrogen atmosphere, raising the temperature to 650 ℃ at the heating rate of 5 ℃/min for high-temperature activation and pore-forming. And directly cooling after the target temperature is reached, and preparing the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 564m 2 Per g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was tested that the adsorption of propylene reached 3.21mmol/g and the adsorption of propane 2.72mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to propylene propane is 1.05 calculated by a Henry coefficient.
The single-component kinetic adsorption experiment of propylene and propane was carried out in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium in 6 minutes, whereas propane reached the adsorption equilibrium in 11 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane is 3.2 calculated by a diffusion coefficient.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. The dynamic adsorption of propylene was 1.65mmol/g, as measured by the breakthrough of propane at 25 minutes and propylene at 32 minutes (per g of adsorbent).
Example 14
The microporous carbon material prepared in this example was the same as in example 13.
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption of ethylene reached 3.43mmol/g and the adsorption of ethane 3.14mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene ethane is 1.06 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium in 5 minutes, whereas ethane reached the adsorption equilibrium in 7 minutes. The dynamic adsorption selectivity of the adsorbent to ethylene ethane reaches 1.3 through the calculation of a diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. The dynamic adsorption of ethylene was 1.74mmol/g, as measured by the breakthrough of ethane starting at 26 minutes and the breakthrough of ethylene starting at 34 minutes (per g of adsorbent).
Example 15
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the rate of 3 ℃/min for reaction for 5h, then directly drying, grinding and tabletting the obtained carbon coke, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the rate of 1 ℃/min, raising the temperature to 650 ℃ at the rate of 5 ℃/min for 2h in the nitrogen atmosphere, carrying out high-temperature activation and pore-forming, and then cooling to prepare the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 695m 2 In g, effective micropore diameter of
A single-component adsorption experiment of propylene and propane was performed in the same manner as in example 1. It was tested that the adsorption of propylene reached 3.35mmol/g and the adsorption of propane 3.19mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to propylene propane is 1.02 calculated by a Henry coefficient.
The single-component kinetic adsorption experiment of propylene and propane was carried out in the same manner as in example 1. It was tested that at 25 ℃ and 100kPa, propylene reached the adsorption equilibrium in 8 minutes, whereas propane reached the adsorption equilibrium in 10 minutes. The dynamic adsorption selectivity of the adsorbent to propylene propane reaches 1.24 through diffusion coefficient calculation.
The breakthrough test of the mixed gas of propylene and propane was carried out in the same manner as in example 1. It was tested that propane started breakthrough at 27 minutes, whereas propylene started breakthrough at 33 minutes (per g of adsorbent), with a dynamic adsorption of 1.71mmol/g propylene.
Example 16
Preparing 0.75mol/L sucrose solution, filling 90% of the sucrose solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programming oven, raising the temperature to 190 ℃ at the heating rate of 3 ℃/min for reaction for 5h, immediately drying, grinding and tabletting the obtained carbon coke directly, transferring the carbon coke into a tubular furnace, controlling the nitrogen flow rate to be 25mL/min, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, raising the temperature to 750 ℃ at the heating rate of 5 ℃/min for keeping for 2h in the nitrogen atmosphere, performing high-temperature activation and pore-forming, and then cooling to prepare the microporous carbon material.
The microporous carbon material prepared in this example had a microporosity of 100% and a specific surface area of 850m 2 Per g, effective micropore diameter of
Single component adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that the adsorption of ethylene reached 4.16mmol/g and the adsorption of ethane 3.84mmol/g at 25 ℃ and 1 bar. The adsorption selectivity of the adsorbent to ethylene ethane is 1.18 calculated by a Henry coefficient.
Single component kinetic adsorption experiments of ethylene and ethane were performed in the same manner as in example 2. It was tested that at 25 ℃ and 100kPa, ethylene reached the adsorption equilibrium at 6 minutes and ethane reached the adsorption equilibrium at 8 minutes. The dynamic adsorption selectivity of the adsorbent to ethylene ethane is 1.3 calculated by a diffusion coefficient.
The breakthrough test of the mixed gas of ethylene and ethane was carried out in the same manner as in example 2. It was tested that ethane started breakthrough at 34 minutes, whereas ethylene started breakthrough at 38 minutes (per g of adsorbent), with a dynamic adsorption of 2.14mmol/g of ethylene.
It should be noted that the above-mentioned embodiments are only for explaining the present application and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as specified within the scope of the claims of the present application and modifications may be made to the present application without departing from the scope and spirit of the present application. Although the present application has been described herein with reference to particular means, materials and embodiments, the present application is not intended to be limited to the particulars disclosed herein, but rather the present application extends to all other methods and applications having the same functionality.
Claims (19)
1. The application of the microporous carbon material in the adsorption separation of olefin and alkane, wherein the preparation method of the microporous carbon material comprises the following steps:
s1: carrying out hydrothermal reaction on a sucrose solution to obtain coke, wherein the sucrose solution is a sucrose aqueous solution, and the concentration of the sucrose solution is 0.5-2.0 mol/L;
s2: carrying out pore-forming treatment on the coke to obtain the microporous carbon material;
wherein in the step S1, the temperature of the hydrothermal reaction is 150-250 ℃ and the time is 3-10 h;
in the step S2, the pore-forming treatment is pyrolysis pore-forming, and the temperature of the pyrolysis pore-forming is 400-800 ℃.
2. The use according to claim 1, wherein in step S1, the concentration of the sucrose solution is 0.5mol/L to 1.0mol/L.
3. The use according to claim 1, wherein in step S1, the temperature of the hydrothermal reaction is 180 ℃ to 200 ℃ and/or the time of the hydrothermal reaction is 5h to 10h.
4. Use according to claim 1, wherein in step S1 the temperature of the hydrothermal reaction is achieved by temperature programming.
5. Use according to claim 4, wherein the temperature-programmed temperature is raised at a rate of 2 ℃/min to 5 ℃/min.
6. The use of claim 1, wherein the pyrolytically induced pore temperature is in the range of 600 ℃ to 800 ℃.
7. The use of claim 1, wherein in the pore-forming process, the pyrolytically formed pores are cooled directly after reaching a target temperature.
8. The use of claim 1, wherein the pyrolytically induced pore temperature is achieved by temperature programming.
9. Use according to claim 8, wherein the temperature programmed rise rate is from 1 ℃/min to 10 ℃/min.
10. The use of claim 8, wherein the pyrolytically induced pore formation is carried out by first increasing the temperature at a rate of 1 ℃/min to 3 ℃/min, and then increasing the temperature at a rate of 5 ℃/min to 8 ℃/min.
11. The use according to any one of claims 1 to 10, wherein in step S2, the pore-forming treatment is performed under the protection of an inert gas; and/or
After drying the coke before step S2, the tablets are ground.
12. Use according to claim 11, wherein the inert gas is one of nitrogen, argon or helium.
13. Use according to claim 11, wherein the inert gas has a gas flow rate of 10-500 mL/min.
14. Use according to claim 11, wherein the inert gas has a gas flow rate of 25-100 mL/min.
15. Use according to any one of claims 1 to 10, wherein the microporous carbon material has a specific surface area of 300m 2 /g-800m 2 (ii)/g; and/or
The microporosity of the microporous carbon material is 80% -100%; and/or
The microporous carbon material has an effective micropore diameter of
And/or
The shape of the microporous carbon material includes at least one of a sphere, a column, a particle, or a membrane.
16. Use according to claim 15, wherein the microporous carbon material has a specific surface area of 400m 2 /g-600m 2 (ii)/g; and/or
The microporosity of the microporous carbon material is 95-100%; and/or
The microporous carbon material has an effective micropore diameter of
17. Use according to any one of claims 1 to 10, wherein the alkane comprises ethane and/or propane and the alkene comprises ethylene and/or propylene.
18. Use according to any one of claims 1 to 10, wherein the temperature of the adsorptive separation is from-5 ℃ to 50 ℃; and/or
In the adsorption separation, the total pressure of the mixed gas containing the olefin and the alkane is 100kPa to 1000kPa.
19. Use according to any one of claims 1 to 10, wherein the adsorptive separation is a kinetic adsorptive separation.
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| CN108311109A (en) * | 2018-02-26 | 2018-07-24 | 华南理工大学 | A kind of molasses adsorbing material and its preparation method and application |
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