CN119565561B - A zeolite for gas separation and its application - Google Patents
A zeolite for gas separation and its application Download PDFInfo
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- CN119565561B CN119565561B CN202510131363.7A CN202510131363A CN119565561B CN 119565561 B CN119565561 B CN 119565561B CN 202510131363 A CN202510131363 A CN 202510131363A CN 119565561 B CN119565561 B CN 119565561B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/105—Removal of contaminants of nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- B01D2257/00—Components to be removed
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- B01D2257/102—Nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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Abstract
The application relates to the technical field of zeolite modification and gas separation, and particularly discloses zeolite for gas separation and application thereof. The zeolite with the excellent gas separation performance is composed of zeolite with different specific particle size distributions, has a short gas diffusion path and a hierarchical pore structure, enables adsorption sites to be fully exposed and reduces gas mass transfer diffusion resistance, and has remarkable separation effect improvement when being applied to gas separation, especially nitrogen/methane separation, carbon dioxide/methane separation and nitrogen/methane/carbon dioxide, and has great significance on methane utilization and recovery.
Description
Technical Field
The application relates to the technical field of zeolite modification and gas separation, in particular to zeolite for gas separation and application thereof.
Background
Methane is the second largest greenhouse gas caused by human activities, the greenhouse effect of which is 28 times (100 years old) that of carbon dioxide, and meanwhile, methane is also an efficient clean fuel and an important chemical raw material, so that research on recovery and utilization of methane has important economic and environmental effects.
The adsorption separation method using zeolite as adsorbent for separating methane and other gases has the characteristics of low energy consumption, flexible operation and the like, and has wide development prospect. However, synthetic and natural zeolites are generally large in size and single in particle size distribution, and have problems of limited gas mass transfer rate, resulting in insufficient zeolite utilization and poor gas separation. Although particle size distribution can be controlled or hierarchical pore structures can be introduced by adding templates, surfactants or acid/alkali post-treatments to improve the aerodynamic diffusion properties of zeolite, its expensive cost and complex process limit its large-scale application.
At present, amplifying the dynamic diffusion rate difference of gases in zeolite to achieve efficient gas separation has become an important research in the fields of zeolite modification and gas separation.
Disclosure of Invention
The object of the present application is to overcome the above-mentioned disadvantages of the prior art and to provide a zeolite for gas separation and its use. The zeolite of the application has excellent gas separation performance, and can realize the high-efficiency separation of mixed gas.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
The present application provides a zeolite for gas separation, the zeolite comprising a first zeolite, a second zeolite and a third zeolite of different particle size distribution;
the average particle size of the first zeolite is A, and A is less than or equal to 200 nm;
the average grain diameter of the second zeolite is B, and B is 200 nm less than or equal to 600nm;
The average particle diameter of the third zeolite is C, C is 600nm < 5 μm or less.
Through a great deal of researches and experiments, the inventor of the application discovers that the zeolite compounded by adopting the first zeolite, the second zeolite and the third zeolite with the specific average particle size ranges has excellent gas separation performance and can realize the high-efficiency separation of mixed gas based on gas diffusion dynamics.
When the first zeolite, the second zeolite and the third zeolite do not use the above average particle size ranges, the difference in kinetic diffusion rates of the zeolite is small, and sieving of methane and other gases cannot be achieved, or separation performance is poor.
The zeolite with excellent gas separation performance has a short gas diffusion path and a hierarchical pore structure, so that adsorption sites are fully exposed and gas mass transfer diffusion resistance is reduced, and when the zeolite is applied to gas separation, the separation effect is obviously improved, and the zeolite has great significance on methane utilization and recovery.
As a preferred embodiment of the zeolite for gas separation according to the present application, the first, second and third zeolite comprises at least one of clinoptilolite, mordenite, 4A zeolite, ZSM-5 zeolite, PHI zeolite. Clinoptilolite and mordenite are typically natural zeolite and synthetic zeolite, 4A zeolite, ZSM-5 zeolite, PHI zeolite are typically synthetic zeolite.
As a preferred embodiment of the zeolite for gas separation according to the present application, the mass ratio of the first zeolite to the second zeolite to the third zeolite is (5-8): (1-4): 1.
When the first zeolite, the second zeolite and the third zeolite adopt the mass ratio, the zeolite obtained by compounding has more excellent gas separation performance, has obvious gas separation effect and has great significance on methane utilization and recovery. If the mass of the first zeolite is lower than the section, the separation gas and methane are difficult to be screened or efficiently screened, and if the mass of the first zeolite is higher than the section, the pressure drop in the adsorption tower is extremely large.
As a preferred embodiment of the zeolite for gas separation according to the present application, the pore volume of the first zeolite is 0.1-0.2 cm 3/g.
As a preferable embodiment of the zeolite for gas separation of the present application, the pore volume of the second zeolite is 0.05-0.1 cm 3/g.
As a preferred embodiment of the zeolite for gas separation according to the present application, the pore volume of the third zeolite is 0.01-0.05 cm 3/g.
When the first zeolite, the second zeolite and the third zeolite adopt the pore volume range, the zeolite has a hierarchical pore structure and a shorter gas diffusion path, so that adsorption sites are fully exposed, gas mass transfer diffusion resistance is reduced, gas is better separated, and the zeolite with the pore volume not in the range has the problems of diffusion limitation, low adsorption capacity, poor nitrogen/methane selectivity and the like, and gas cannot be separated.
As a preferred embodiment of the zeolite for gas separation according to the present application, the zeolite having a particle size of more than 20 μm is ball-milled by a ball mill to prepare a first zeolite, a second zeolite and a third zeolite having different particle size distributions;
The mass ratio of the zeolite to the ball-milling beads is 1 (3-30);
The ball milling beads comprise small beads with the particle size of 1mm, medium beads with the particle size of 5 mm and large beads with the particle size of 10 mm, wherein the weight ratio of the small beads to the medium beads to the large beads is (5-7): (2-3): (1-2).
The small, medium and large beads of the application can be ball milled to obtain the first, second and third zeolite with specific particle size distribution, so as to obtain more excellent gas separation performance.
In some embodiments, the ball milling is dry milling or wet milling;
preferably, the ball milling is wet milling, and the adopted solvent comprises at least one of ethanol, methanol and water, and the mixing ratio of the zeolite and the solvent is 25-100 g/L.
The application also provides application of the zeolite in gas separation.
The application also provides a gas separation method comprising separating a gas comprising at least one of methane and a separation gas having the same diameter and characteristics as methane kinetics by using the zeolite.
As a preferred embodiment of the gas separation method of the present application, the separation gas includes carbon dioxide and nitrogen;
The method comprises the steps of separating nitrogen from methane and separating carbon dioxide from methane, wherein the volume ratio of methane to separating gas is 1:1, the total flow rate of methane flow rate and separating gas flow rate is 2-20 sccm (standard cubic centimeters per minute), the volume ratio of nitrogen to methane to carbon dioxide is 5:30:65 when separating nitrogen from methane from carbon dioxide, the total flow rate is 5-10 sccm, and the flow rate of purge gas is one of argon and helium and is 5-30 sccm.
When the zeolite with excellent gas separation performance is applied to gas separation, especially nitrogen/methane separation, carbon dioxide/methane separation and nitrogen/methane/carbon dioxide, the separation effect is obviously improved, and the zeolite has great significance on methane utilization and recovery.
Compared with the prior art, the application has the following beneficial effects:
The application provides a zeolite for gas separation and application thereof, wherein the zeolite with excellent gas separation performance is composed of zeolite with different specific particle size distribution, the zeolite has a short gas diffusion path and a hierarchical pore structure, so that adsorption sites are fully exposed and gas mass transfer diffusion resistance is reduced, and when the zeolite is applied to gas separation, especially nitrogen/methane separation, carbon dioxide/methane separation and nitrogen/methane/carbon dioxide, the separation effect is obviously improved, and the zeolite has great significance for methane utilization and recovery.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of the zeolite of example 1;
FIG. 2 is a graph showing the separation performance results of the zeolite of example 1 in a nitrogen/methane mixed gas;
FIG. 3 is a graph showing the separation performance of the zeolite of example 1 in a nitrogen/methane/carbon dioxide mixed gas.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to the accompanying drawings and specific embodiments.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, the materials, reagents and the like used were commercially available, and the component materials used in each parallel experiment were the same.
In the following examples and comparative examples:
The synthesis of mordenite, namely mixing raw materials of tetraethyl silicate, aluminum sulfate, sodium hydroxide and water according to the mass ratio of 14:1.4:1:20, magnetically stirring for 24 h, transferring into a polytetrafluoroethylene reaction kettle, reacting for 6 days at 180 ℃, and cleaning and drying after the reaction is finished to obtain mordenite.
Example 1
The present example provides a zeolite having utility for gas separation:
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 6:3:1, the mass ratio of mordenite to ball-milling beads is 1:20, the ball-milling time is 4 hours, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is not more than 80 and less than 24A and not more than 150 and nm, the particle size of the second zeolite is B, the particle size of the second zeolite is not more than 400 and not more than 520 and nm, the particle size of the third zeolite is C, the particle size of the third zeolite is not more than 1 mu m and not more than 2 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 6:3:1, the pore volume of the first zeolite is 0.2cm 3/g, the pore volume of the second zeolite is 0.1cm 3/g, and the pore volume of the third zeolite is 0.05cm 3/g.
A Scanning Electron Microscope (SEM) with zeolite for gas separation was obtained in example 1 above as shown in fig. 1.
Example 2
The present example provides a zeolite having utility for gas separation:
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 5:3:2, the mass ratio of mordenite to ball-milling beads is 1:20, the ball-milling time is 5h, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is not more than 120 nm, the particle size of the first zeolite is not more than 180 nm, the particle size of the second zeolite is B, the particle size of the second zeolite is not more than 450 nm, the particle size of the second zeolite is not more than 500 nm, the particle size of the third zeolite is C, the particle size of the third zeolite is not more than 1.2 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 5:4:1, the pore volume of the first zeolite is 0.14cm 3/g, the pore volume of the second zeolite is 0.07cm 3/g, and the pore volume of the third zeolite is 0.03cm 3/g.
Example 3
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 7:2:1, the mass ratio of mordenite to ball-milling beads is 1:20, the ball-milling time is 4 hours, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is not more than 80 and not more than 84 and not more than 120 nm, the particle size of the second zeolite is B, the particle size of the second zeolite is not less than 380 and not more than 4 and not more than 450 and not more than 4, the particle size of the third zeolite is C, the particle size of the third zeolite is not more than 600 and not more than 72 and not more than 1.5 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 7:2:1, the pore volume of the first zeolite is 0.18cm 3/g, the pore volume of the second zeolite is 0.09cm 3/g, and the pore volume of the third zeolite is 0.04cm 3/g.
Example 4
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 6:3:1, the mass ratio of mordenite to ball-milling beads is 1:5, the ball-milling time is 4 hours, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is less than or equal to 150nm and less than or equal to 200nm, the particle size of the second zeolite is B, the particle size of the second zeolite is less than or equal to 480nm and less than or equal to 600 nm, the particle size of the third zeolite is C, the particle size of the third zeolite is less than or equal to 3 mu m and less than or equal to 5 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 5:4:1, the pore volume of the first zeolite is 0.13cm 3/g, the pore volume of the second zeolite is 0.06cm 3/g, and the pore volume of the third zeolite is 0.03cm 3/g. .
Example 5
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 6:3:1, the mass ratio of mordenite to ball-milling beads is 1:5, the ball-milling time is 4 hours, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is not more than 80nm and not more than 120 nm, the particle size of the second zeolite is B, the particle size of the second zeolite is not more than 350nm and not more than 500 nm, the particle size of the third zeolite is C, the particle size of the third zeolite is not more than 800nm and not more than 1.5 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 6:3:1, the pore volume of the first zeolite is 0.17cm 3/g, the pore volume of the second zeolite is 0.09cm 3/g, and the pore volume of the third zeolite is 0.01cm 3/g.
Example 6
1. Adding mordenite and ball-milling beads into a ball-milling tank, wherein the weight ratio of small beads (1 mm) to medium beads (5 mm) to large beads (10 mm) is 6:3:1, the mass ratio of mordenite to ball-milling beads is 1:30, the ball-milling time is 4 hours, and the rotating speed of the ball-milling machine is 600 rpm.
2. The ball milling sample is recovered, and the first zeolite, the second zeolite and the third zeolite are collected to form the zeolite for gas separation in the embodiment of the application, wherein the particle size of the first zeolite is A, the particle size of the second zeolite is less than or equal to 80nm and less than or equal to 150nm, the particle size of the second zeolite is B, the particle size of the second zeolite is less than or equal to 300nm and less than or equal to 400nm, the particle size of the third zeolite is C, the particle size of the third zeolite is less than or equal to 700nm and less than or equal to 1.4 mu m, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 8:1:1, the pore volume of the first zeolite is 0.1cm 3/g, the pore volume of the second zeolite is 0.05cm 3/g, and the pore volume of the third zeolite is 0.01cm 3/g.
Comparative examples 1 to 8
Comparative examples 1 to 8 differ from example 1 in that table 1;
TABLE 1
The difference between this and example 1 is that comparative example 1 uses a ball mill rotation speed of 200 rpm, and the remaining parameters are the same as example 1.
The difference compared to example 1 is that comparative example 2 uses a ball milling time of 3h, and the remaining parameters are the same as example 1.
The difference compared to example 1 is that comparative example 3 uses ball-milled beads and zeolite in a mass ratio of 35:1, and the remaining parameters are the same as in example 1.
The difference compared to example 1 is that the weight ratio of the small beads (1 mm) to the medium beads (5 mm) to the large beads (10 mm) used in comparative example 4 was 3:5:2, and the other parameters were the same as in example 1.
The difference compared to example 1 is that the weight ratio of the small beads (1 mm) to the medium beads (5 mm) to the large beads (10 mm) used in comparative example 5 was 1:8:1, and the other parameters were the same as in example 1.
The difference compared to example 1 is that the ball milling time of comparative example 6 is 2 h, and the remaining parameters are the same as example 1.
The difference compared to example 1 is that comparative example 7 uses a ball milling time of 15 h and the remaining parameters are the same as example 1.
In comparison with example 1, the difference was that comparative example 8 uses water as a ball milling medium, the mixing ratio of zeolite and water was 100 g/L, and the remaining parameters were the same as in example 1.
Test examples, examples 1-6 and comparative examples 1-8 zeolite applications in nitrogen/methane gas separation applications
The zeolite prepared in examples 1-6 and comparative examples 1-8 was loaded into a gas permeation column, and the specific test method was that the zeolite was first vacuum activated at 300 ℃ for 10 h hours, then gas was dispensed at a gas volume composition of nitrogen: methane=1:1, total flow rate of 2mL, argon was used as a reference gas, and the mixed gas was introduced into the permeation column, and the end was analyzed by online mass spectrometry to obtain a multicomponent permeation curve.
The results are shown in Table 2.
TABLE 2
The results are shown in Table 2;
the test results of example 1 show that the methane purity can be increased from 50% to 75%, and the experimental results are shown in fig. 2.
The test results of example 2 show that methane purity can be increased from 50% to 70%.
The test results of example 3 show that methane purity can be increased from 50% to 78%.
The test results of example 4 show that methane purity can be increased from 50% to 72%.
The test results of example 5 show that methane purity can be increased from 50% to 70%.
The test results of example 6 show that methane purity can be increased from 50% to 65%.
The ball milling rotation speed of comparative example 1 is slower, the particle size distribution of the first zeolite, the second zeolite and the third zeolite is 5-20 μm, the other parameters are the same as those of example 1, and the methane and nitrogen penetrate simultaneously due to the larger particle size, so that the purity of the methane is hardly improved.
The ball milling time of comparative example 2 is shorter than that of example 1, the particle diameters of the first zeolite, the second zeolite and the third zeolite are respectively 400 nm-500 nm, 400-500 nm, 800-500 nm and 1 μm, the rest parameters are the same as those of example 1, mass transfer limitation still exists, methane and nitrogen are penetrated at the same time, and the purity of methane is almost not improved.
The mass ratio of ball milling beads to zeolite adopted in comparative example 3 is 35:1, the particle sizes of the first zeolite, the second zeolite and the third zeolite are very narrow, the particle sizes are respectively 80 nm-150 nm,80 nm-150 nm and 800 nm-1 μm, the rest parameters are the same as those in example 1, a large pressure drop exists in a penetrating column, methane and nitrogen are almost penetrated at the same time, and the methane purity is only slightly improved.
The ball-milling beads of comparative example 4 had a high bead ratio, the mass ratio of the first zeolite, the second zeolite, and the third zeolite of 1:1:1, the rest parameters are the same as in example 1, mass transfer limitation still exists, methane and nitrogen penetrate simultaneously, and the purity of methane is hardly improved.
The ball-milling beads of comparative example 5 are mainly medium beads, the mass ratio of the first zeolite to the second zeolite to the third zeolite is 1:8:1, the rest parameters are the same as those of example 1, mass transfer limitation exists, methane and nitrogen penetrate almost simultaneously, and the purity of methane is only slightly improved.
The comparative example 6 was insufficient in ball milling time, the pore volume of the first zeolite was 0.08cm 3/g, the remaining parameters were the same as in example 1, the adsorption site exposure was insufficient, methane nitrogen was simultaneously penetrated, and the methane purity was only slightly improved.
Comparative example 7 has a too long ball milling time, the pore volume of the second zeolite is 0.02cm 3/g, the other parameters are the same as those of example 1, the problem of poor zeolite crystallinity exists, methane and nitrogen penetrate simultaneously, and the purity of methane is hardly improved.
Comparative example 8 the pore volume of the third zeolite was 0.15cm 3/g using water as the ball milling medium, the zeolite lost the nitrogen methane selectivity, methane nitrogen penetrated simultaneously, and the methane purity was hardly improved.
Similarly, the separation performance results of the zeolite of example 1 in a nitrogen/methane/carbon dioxide mixed gas are shown in fig. 3.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present application.
Claims (5)
1. A zeolite for gas separation, wherein the zeolite comprises a first zeolite, a second zeolite, and a third zeolite having different particle size distributions;
the average particle size of the first zeolite is A, and A is less than or equal to 200 nm;
the average grain diameter of the second zeolite is B, and B is 200 nm less than or equal to 600nm;
the average particle diameter of the third zeolite is C, C less than 600nm and less than or equal to 5 mu m;
The first zeolite, the second zeolite and the third zeolite comprise at least one of clinoptilolite, mordenite, 4A zeolite, ZSM-5 zeolite and PHI zeolite;
the mass ratio of the first zeolite to the second zeolite to the third zeolite is (5-8): (1-4): 1;
The pore volume of the first zeolite is 0.1-0.2 cm 3/g;
the pore volume of the second zeolite is 0.05-0.1 cm 3/g;
The pore volume of the third zeolite is 0.01-0.05 cm 3/g.
2. The zeolite for gas separation according to claim 1, wherein the zeolite having a particle size of more than 20 μm is ball-milled by ball-milling to prepare a first zeolite, a second zeolite and a third zeolite having different particle size distributions;
The mass ratio of the zeolite to the ball-milling beads is 1 (3-30);
the ball-milling beads comprise small beads with the particle size of 1 mm, medium beads with the particle size of 5 mm and large beads with the particle size of 10 mm;
the weight ratio of the small beads to the medium beads to the large beads is (5-7): (2-3): (1-2).
3. Use of a zeolite according to claim 1 or 2 in gas separation.
4. A gas separation process comprising separating a gas comprising methane and a separation gas having the same kinetic diameter and characteristics as methane using the zeolite of claim 1 or 2.
5. The gas separation process of claim 4, wherein the separation gas comprises carbon dioxide and/or nitrogen;
The method comprises the steps of separating nitrogen from methane and separating carbon dioxide from methane, wherein the volume ratio of methane to separating gas is 1:1, the total flow rate of methane flow rate and separating gas flow rate is 2-20 sccm, the volume ratio of nitrogen to methane to carbon dioxide is 5:30:65, the total flow rate is 5-10 sccm, and the flow rate of purge gas is one of argon and helium and is 5-30 sccm.
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