CN113277927A - Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane - Google Patents

Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane Download PDF

Info

Publication number
CN113277927A
CN113277927A CN202110597994.XA CN202110597994A CN113277927A CN 113277927 A CN113277927 A CN 113277927A CN 202110597994 A CN202110597994 A CN 202110597994A CN 113277927 A CN113277927 A CN 113277927A
Authority
CN
China
Prior art keywords
ssz
butane
isobutane
molecular sieve
adsorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110597994.XA
Other languages
Chinese (zh)
Other versions
CN113277927B (en
Inventor
林贻超
陈亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN202110597994.XA priority Critical patent/CN113277927B/en
Publication of CN113277927A publication Critical patent/CN113277927A/en
Application granted granted Critical
Publication of CN113277927B publication Critical patent/CN113277927B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—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
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating

Abstract

The invention discloses an application of a microporous molecular sieve in adsorption and separation of n-butane and isobutane. Wherein the microporous molecular sieve is an SSZ-13 molecular sieve with a CHA type topological structure, and the structure of the SSZ-13 molecular sieve is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure. The invention also discloses a normal butane/isobutane adsorption separation material, a device and a corresponding method for adsorbing and separating normal butane and isobutane. The SSZ-13 molecular sieve provided by the inventionThe adsorption device can selectively adsorb a large amount of n-butane and does not adsorb isobutane basically, so that the SSZ-13 molecular sieve is filled in a fixed bed adsorption separation device to realize the efficient separation of n-butane and isobutane, and the adsorption device can be used at normal temperature and normal pressure, so that the adsorption device is more energy-saving and environment-friendly, and the molecular sieve is simple and convenient to regenerate and utilize and has good stability.

Description

Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane
Technical Field
The invention belongs to the field of petrochemical industry, relates to application of a microporous molecular sieve in adsorption and separation of n-butane and isobutane, and particularly relates to a separation material for n-butane and isobutane and an adsorption and separation method.
Background
The great attention is paid to how to fully and reasonably utilize the byproduct resources by generating a large amount of C4 hydrocarbons (normal butane and isobutane) in the petroleum refining process, and the separation of light hydrocarbons is one of the most energy-intensive and demanding processes in the petroleum, natural gas and fuel industries. The separation of n-paraffins (n-butane, n-pentane), mainly from branched and cyclic paraffins, allows the production of highly efficient feedstocks in refineries, i.e. gasolines with a high octane number or diesel with a high cetane number. In practice, the octane number of gasoline-type fuels is directly related to the performance of the engine, and branched isomers with higher octane numbers are typically added to gasoline, while less valuable linear isomers are removed. In contrast, in the case of diesel fuel, linear paraffins are essential components of diesel fuel, and therefore, selective separation of branched paraffins from linear paraffins is important. Meanwhile, the C4 hydrocarbon is processed into various liquid fuels or additives such as alkylate oil and liquefied gasoline for vehicles, and the like, so that the application value is high. At present, the separation is mainly carried out by adopting the traditional rectification method, however, because the boiling points of normal butane (boiling point, -0.5 ℃ C.) and isobutane (boiling point, -11.73 ℃ C.) are close (only about 10 ℃ C difference), the process of separating the normal butane and the isobutane by adopting the rectification method is very energy-consuming, and therefore, the research on environment-friendly new technology for separating the normal butane and the isobutane is needed.
Disclosure of Invention
In view of the above technical situation, the main object of the present invention is to provide an application of a microporous molecular sieve in adsorption and separation of n-butane and isobutane, so as to overcome the disadvantages in the prior art.
The invention also aims to provide an n-butane/isobutane adsorption and separation material and an adsorption and separation method.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides application of a microporous molecular sieve in adsorption and separation of n-butane and isobutane, wherein the microporous molecular sieve is an SSZ-13 molecular sieve with a CHA type topological structure, and the structure of the SSZ-13 molecular sieve is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure.
Further, the SSZ-13 molecular sieve has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption separation material at least can selectively adsorb n-butane and not isobutane.
Further, the framework of the SSZ-13 molecular sieve contains Al atoms, thereby having negative charges, and the counter ions of the negative charges of the framework of the SSZ-13 molecular sieve include but are not limited to Na+、NH4 +、H+、Fe3+Or Cu2+And the like.
The embodiment of the invention also provides a normal butane/isobutane adsorption and separation material, the normal butane/isobutane adsorption and separation material is an SSZ-13 molecular sieve with a CHA type topological structure, and the structure of the SSZ-13 molecular sieve is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure; the n-butane/isobutane adsorption and separation material has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption and separation material at least can selectively adsorb n-butane and not isobutane.
The embodiment of the invention also provides a normal butane/isobutane adsorption and separation device, wherein the device is filled with fillers containing the normal butane/isobutane adsorption and separation material.
The embodiment of the invention also provides a method for adsorbing and separating normal butane and isobutane, which comprises the following steps:
and introducing the mixed gas containing n-butane and isobutane into the n-butane/isobutane adsorption and separation device, so that the n-butane in the mixed gas is completely adsorbed by the SSZ-13 molecular sieve in the n-butane/isobutane adsorption and separation device, and the efficient separation of the n-butane and the isobutane is realized.
Compared with the prior art, the method for separating the n-butane/isobutane mixture by adopting the SSZ-13 molecular sieve as the adsorption material has at least the following unexpected beneficial effects:
1) the SSZ-13 molecular sieve provided by the invention can selectively adsorb a large amount of n-butane, but does not basically adsorb isobutane, so that the high-efficiency separation of n-butane and isobutane can be realized by filling the SSZ-13 molecular sieve in a fixed bed adsorption separation device, and the separation of n-butane and isobutane can be performed at normal temperature and normal pressure without additional refrigeration compared with a rectification separation method aiming at the separation of n-butane and isobutane, so that the energy conservation and environmental protection are better;
2) the SSZ-13 molecular sieve has excellent n-butane and isobutane separation performance, wherein the purity of isobutane can reach more than 99 percent, and the purity of n-butane can reach more than 95 percent;
3) the SSZ-13 molecular sieve has high n-butane adsorption capacity of more than 50cm3g-1；
4) The SSZ-13 molecular sieve is simple and convenient to regenerate and has good stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view showing the construction of an apparatus for adsorptive separation of a n-butane/isobutane mixture in an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of the crystal structure of an SSZ-13 molecular sieve, an n-butane/isobutane adsorbing and separating material, in an exemplary embodiment of the present invention;
FIG. 3 is a schematic diagram of a standard XRD diffraction peak of SSZ-13 molecular sieve, an n-butane/isobutane adsorbing and separating material, in an exemplary embodiment of the present invention;
FIG. 4 is a graph showing the adsorption profiles of n-butane and isobutane for Na-SSZ-13 prepared in example 1 of the present invention;
FIG. 5 is NH prepared in example 2 of the present invention4-adsorption profile of n-butane and isobutane of SSZ-13;
FIG. 6 is a graph of the adsorption of n-butane and isobutane for H-SSZ-13 prepared in example 3 of the present invention;
FIG. 7 is a graph of the adsorption of n-butane and isobutane for Cu-SSZ-13 prepared in example 4 of the present invention;
FIG. 8 is a graph of the adsorption of n-butane and isobutane for Fe-SSZ-13 prepared in example 5 of the present invention;
FIG. 9 is a graph showing the breakthrough of a mixed n-butane/isobutane gas of Na-SSZ-13 molecular sieves in example 6 of the present invention.
Detailed Description
In view of the above technical defects, the inventors of the present invention have made extensive experimental research and extensive practice for a long time to provide a technical solution of the present invention, which mainly provides an SSZ-13 microporous molecular sieve applicable to adsorption and separation of n-butane and isobutane, and the SSZ-13 molecular sieve having CHA topology can selectively adsorb n-butane in a large amount without substantially adsorbing isobutane. The technical solution, its implementation and principles, etc. will be further explained as follows.
As one aspect of the technical scheme, the invention relates to the application of a microporous molecular sieve in adsorption and separation of n-butane and isobutane, wherein the microporous molecular sieve is an SSZ-13 molecular sieve with a CHA-type topological structure, and the structure of the SSZ-13 molecular sieve is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional crossed pore channel structure, the pore channel size is 3-5 nm, the specific crystal structure is shown in figure 2, and the standard XRD diffraction peak is shown in figure 3.
Further, the SSZ-13 molecular sieve has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption separation material at least can selectively adsorb n-butane and not isobutane.
In some embodiments of the present invention, the SSZ-13 molecular sieve is negatively charged due to the Al atoms contained in the framework, and the counter ion for the negative framework charge of the SSZ-13 molecular sieve may include, but is not limited to, Na+、NH4 +、H+、Fe3+Or Cu2+And the like.
Accordingly, the SSZ-13 molecular sieve is represented by Na-SSZ-13, H-SSZ-13, NH4Any one or a combination of two or more of-SSZ-13, Fe-SSZ-13, Cu-SSZ-13, etc., but not limited thereto.
Further, the SSZ-13 molecular sieve is preferably Na-SSZ-13.
Among them, the preparation method of Na-SSZ-13 molecular sieve can be referred to patent CN 109110777A, NH4SSZ-13 can be prepared by reference to Journal of Catalysis 300(2013)20-29, and Cu-SSZ-13 can be prepared by reference to Journal of Catalysis 300(2013) 20-29.
As another aspect of the technical scheme of the invention, the invention relates to an n-butane/isobutane adsorption and separation material, wherein the n-butane/isobutane adsorption and separation material is an SSZ-13 molecular sieve with a CHA-type topological structure, and the structure of the SSZ-13 molecular sieve is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure, and the pore channel size is 3-5 nm; the n-butane/isobutane adsorption and separation material has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption and separation material at least can selectively adsorb n-butane and not isobutane.
In some embodiments of the present invention, the SSZ-13 molecular sieve is negatively charged due to the Al atoms contained in the framework, and the counter ion for the negative framework charge of the SSZ-13 molecular sieve may include, but is not limited to, Na+、NH4 +、H+、Fe3+Or Cu2+And the like.
Accordingly, the SSZ-13 molecular sieve is represented by Na-SSZ-13, H-SSZ-13, NH4Any one or a combination of two or more of-SSZ-13, Fe-SSZ-13, Cu-SSZ-13, etc., but not limited thereto.
Further, the SSZ-13 molecular sieve is preferably Na-SSZ-13.
In another aspect of the technical scheme of the invention, the invention relates to a normal butane/isobutane adsorption and separation device, wherein a filler containing the normal butane/isobutane adsorption and separation material is filled in the device.
Further, the n-butane/isobutane adsorption and separation device is a fixed bed adsorption and separation device, and the filler is filled in the fixed bed.
Further, the filler is SSZ-13 molecular sieve, or a mixture or a compound containing the SSZ-13 molecular sieve.
In view of the above, the inventors further packed the SSZ-13 molecular sieve in a fixed bed, and successfully separated the gas mixture of n-butane and isobutane by a fixed bed adsorption separation technique. Compared with a rectification separation method, the method for separating the normal butane and the isobutane has the advantages that extra refrigeration is not needed in the fixed bed adsorption separation, and the fixed bed adsorption separation can be carried out at normal temperature and normal pressure, so that the method is more energy-saving and environment-friendly.
Namely, the technical scheme provided by the invention is as follows: the fixed bed containing SSZ-13 molecular sieve is used for adsorbing and separating the gas mixture of normal butane and isobutane. The device has a structure shown in figure 1, n-butane and isobutane pass through a fixed bed provided with an SSZ-13 molecular sieve, n-butane in mixed gas is completely adsorbed by the SSZ-13 due to selective adsorption, pure isobutane is collected through the fixed bed, after adsorption saturation, the introduction of the mixed gas is stopped, the n-butane adsorbed by the SSZ-13 molecular sieve in the fixed bed is released through a heating method, pure n-butane is obtained, and meanwhile, the regeneration of an SSZ-13 adsorbent is realized.
Accordingly, another aspect of the embodiments of the present invention also provides a method for adsorptive separation of n-butane and isobutane, which includes:
and introducing the mixed gas containing n-butane and isobutane into the n-butane/isobutane adsorption and separation device, so that the n-butane in the mixed gas is completely adsorbed by the SSZ-13 molecular sieve in the n-butane/isobutane adsorption and separation device, and the efficient separation of the n-butane and the isobutane is realized.
Further, the method further comprises: the method releases the n-butane adsorbed by the SSZ-13 molecular sieve in the fixed bed by adopting a heating method to obtain pure n-butane and simultaneously realizes the regeneration of the SSZ-13 molecular sieve.
Through the experiments, the SSZ-13 molecular sieve can selectively adsorb a large amount of n-butane (high n-butane adsorption capacity, more than 50 cm)3g-1) And isobutane is not substantially adsorbed, so that high-efficiency separation of n-butane and isobutane can be realized by filling the SSZ-13 molecular sieve in the fixed bed adsorption separation device. Wherein the purity of the isobutane can reach more than 99 percent, and the purity of the normal butane can reach more than 95 percent.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
Preparation of Na-SSZ-13 and adsorption performance of n-butane and isobutane
The Na-SSZ-13 molecular sieve is synthesized by the preparation method of the patent CN 109110777A, which comprises the following steps:
first, 1.658g of sodium metaaluminate (aluminum source) was mixed with 24.14g of pure water and dissolved completely, and then 1.100g of sodium hydroxide was added thereto and stirred for 10 minutes to dissolve completely. Then 2.793g choline chloride was added, stirred for 15 minutes, then 16.88g 25 wt% N, N was added,n-trimethyl-1-amantadine cation aqueous solution is stirred strongly to mix completely, and 40.0g of LUDOX-AS-30 silica sol (silicon source) is added dropwise under the condition of strong stirring. Stirring for 20 hours at room temperature, finally transferring the colloid into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel high-pressure reaction kettle into a 140 ℃ oven and keeping the stainless steel high-pressure reaction kettle for 14 days, collecting the product in a filtering mode, washing the product until the filtrate is neutral, putting the product into the 100 ℃ oven and drying the product for 12 hours, and then calcining the product in a tubular furnace at 550 ℃ for 8 hours to remove a template agent, thus obtaining the Na-SSZ-13 molecular sieve. The adsorption properties of n-butane and isobutane of the prepared Na-SSZ-13 are shown in FIG. 4. The adsorption quantities of n-butane and isobutane of Na-SSZ-13 were 56.9cm at 1000mbar, respectively3g-1And 1.9cm3 g-1。
Example 2
NH4Preparation of-SSZ-13 and adsorption performance of n-butane and isobutane
Preparation of NH according to the method reported in the Journal of Catalysis 300(2013)20-294-SSZ-13, in particular: 1g of Na-SSZ-13 was added to 0.1M NH4NO3Stirring the solution (50mL) at 80 ℃ for 8h, centrifuging and drying to obtain NH4-SSZ-13. Preparation of NH4The adsorption behavior of n-butane and isobutane of SSZ-13 is shown in FIG. 5, NH at 1000mbar4The adsorption amounts of n-butane and isobutane of-SSZ-13 were 36.6cm respectively3g-1And 1.4cm3g-1。
Example 3
Preparation of H-SSZ-13 and adsorption performance of n-butane and isobutane
NH prepared in example 24-SSZ-13 is placed in a muffle furnace and calcined at 550 ℃ for 2H to obtain H-SSZ-13. The adsorption properties of n-butane and isobutane of the prepared H-SSZ-13 are shown in FIG. 6, and the adsorption amounts of n-butane and isobutane of the H-SSZ-13 are 50.4cm at 1000mbar3g-1And 2.6cm3g-1。
Example 4
Preparation of Cu-SSZ-13 and adsorption performance of n-butane and isobutane
According to the Journal of catalysiss 300(2013)20-29, specifically: reacting NH4SSZ-13 to 0.1M CuSO4Stirring the solution at 80 deg.C for 8 hr, centrifuging, drying at 100 deg.C for 8 hr, grinding, and calcining at 550 deg.C for 8 hr. The adsorption properties of n-butane and isobutane of the prepared Cu-SSZ-13 are shown in FIG. 7, and the adsorption amounts of n-butane and isobutane of the Cu-SSZ-13 are 52.0cm at 1000mbar3g-1And 3.7cm3g-1。
Example 5
Preparation of Fe-SSZ-13 and adsorption performance of n-butane and isobutane
The preparation process of the Fe-SSZ-13 molecular sieve comprises the following steps: the H-SSZ-13 molecular sieve of example 3 was added to 0.1M CuSO4Stirring the solution at 80 deg.C under nitrogen protection for 6h, cooling, centrifuging, drying at 80 deg.C, vacuum drying for 8h, grinding, and calcining at 550 deg.C for 2 h. The adsorption properties of the prepared Fe-SSZ-13 butane and isobutane are shown in FIG. 8, and the adsorption amounts of normal butane and isobutane of Fe-SSZ-13 are 40.8cm at 1000mbar respectively3g-1And 1.5em3g-1。
Example 6
N-butane/Isobutane breakthrough test for Na-SSZ-13
The inventor fills the Na-SSZ-13 molecular sieve packing into the device shown in figure 1 and carries out the n-butane/isobutane mixed gas penetration experiment. As a result, as shown in FIG. 9, isobutane penetrated the sample rapidly, while n-butane took 40 minutes to penetrate the sample, since Na-SSZ-13 molecular sieve did not adsorb isobutane substantially, but adsorbed n-butane in a large amount. Breakthrough experiments showed that the gas collected in the first 40 minutes was pure isobutane (greater than 99% purity). In addition, n-butane adsorbed by the Na-SSZ-13 molecular sieve can be desorbed by a heating method to obtain n-butane (the purity is more than 95 percent). Therefore, the high-efficiency separation of n-butane/isobutane can be realized by a simple process.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. The application of the microporous molecular sieve in adsorption and separation of n-butane and isobutane comprises the microporous molecular sieve SSZ-13 with a CHA type topological structure, wherein the structure of the SSZ-13 is formed by AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure.
2. Use according to claim 1, characterized in that: the SSZ-13 molecular sieve has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption separation material at least can selectively adsorb n-butane but not isobutane.
3. Use according to claim 1, characterized in that: the size of the pore channel contained in the three-dimensional cross pore channel structure is 3-5 nm.
4. Use according to claim 1, characterized in that: the framework of the SSZ-13 molecular sieve contains Al atoms so as to have negative charges, and the counter ions of the negative charges of the framework of the SSZ-13 molecular sieve comprise Na+、NH4 +、H+、Fe3+Or Cu2+Preferably, the SSZ-13 molecular sieve comprises Na-SSZ-13, H-SSZ-13, NH4Any one of-SSZ-13, Fe-SSZ-13, Cu-SSZ-13One or a combination of two or more, particularly preferably Na-SSZ-13.
5. The n-butane/isobutane adsorption and separation material is characterized by being an SSZ-13 molecular sieve with a CHA-type topological structure, wherein the structure of the SSZ-13 molecular sieve is AlO4And SiO4The tetrahedrons are connected end to end through oxygen atoms and are orderly arranged into an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross pore channel structure; the n-butane/isobutane adsorption and separation material has n-butane and isobutane separation performance, and the n-butane/isobutane adsorption and separation material at least can selectively adsorb n-butane and not isobutane.
6. The n-butane/isobutane adsorbing and separating material according to claim 5, characterized in that: the size of the pore channel contained in the three-dimensional cross pore channel structure is 3-5 nm.
7. The n-butane/isobutane adsorbing and separating material according to claim 5, characterized in that: the framework of the SSZ-13 molecular sieve contains Al atoms so as to have negative charges, and the counter ions of the negative charges of the framework of the SSZ-13 molecular sieve comprise Na+、NH4 +、H+、Fe3+Or Cu2+Preferably, the SSZ-13 molecular sieve comprises Na-SSZ-13, H-SSZ-13, NH4Any one or a combination of two or more of-SSZ-13, Fe-SSZ-13 and Cu-SSZ-13, and particularly preferably Na-SSZ-13.
8. An n-butane/isobutane adsorbing-separating apparatus, characterized in that a filler containing the n-butane/isobutane adsorbing-separating material according to any one of claims 5 to 7 is filled in the apparatus.
9. The n-butane/isobutane adsorption-separation apparatus according to claim 8, characterized in that: the n-butane/isobutane adsorption separation device is a fixed bed adsorption separation device, and the packing is filled in the fixed bed, preferably, the packing comprises an SSZ-13 molecular sieve or a compound containing the SSZ-13 molecular sieve.
10. A method for adsorbing and separating normal butane and isobutane is characterized by comprising the following steps:
introducing a mixed gas containing n-butane and isobutane into the n-butane/isobutane adsorption and separation device according to claim 8 or 9, so that n-butane in the mixed gas is completely adsorbed by the SSZ-13 molecular sieve in the n-butane/isobutane adsorption and separation device, thereby realizing the efficient separation of n-butane and isobutane;
preferably, the method further comprises: and releasing the n-butane adsorbed by the SSZ-13 molecular sieve in the fixed bed by adopting a heating method to obtain pure n-butane and realize the regeneration of the SSZ-13 molecular sieve.
CN202110597994.XA 2021-05-28 2021-05-28 Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane Active CN113277927B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110597994.XA CN113277927B (en) 2021-05-28 2021-05-28 Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110597994.XA CN113277927B (en) 2021-05-28 2021-05-28 Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane

Publications (2)

Publication Number Publication Date
CN113277927A true CN113277927A (en) 2021-08-20
CN113277927B CN113277927B (en) 2022-08-16

Family

ID=77282470

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110597994.XA Active CN113277927B (en) 2021-05-28 2021-05-28 Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane

Country Status (1)

Country Link
CN (1) CN113277927B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113976177A (en) * 2021-11-26 2022-01-28 华东理工大学 Eutectic solvent and preparation method and application thereof
CN114307536A (en) * 2022-03-02 2022-04-12 山东神驰石化有限公司 N-butane and iso-butane separating tower in n-butane isomerization

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1195655A (en) * 1997-04-04 1998-10-14 傅焕斌 Adsorption separation method for liquefied butagas isomer
US6022398A (en) * 1997-12-31 2000-02-08 Korea Institute Of Energy Research Adsorption separation and purification apparatus and process for high purity isobutane production
CN101171213A (en) * 2005-03-11 2008-04-30 环球油品公司 Processes for the isomerization of normal butane to isobutane
CN109110777A (en) * 2017-06-22 2019-01-01 中国科学院宁波材料技术与工程研究所 A kind of synthetic method of SSZ-13 molecular sieve
US20190329214A1 (en) * 2018-04-30 2019-10-31 The Regents Of The University Of Colorado, A Body Corporate Functionalization of zeolites
CN111514929A (en) * 2019-02-03 2020-08-11 周跃 Cu-SSZ-13 catalyst and H-SSZ-13 molecular sieve with double aluminum centers as well as preparation method and application thereof
CN111592008A (en) * 2020-06-12 2020-08-28 浙江浙能技术研究院有限公司 Method for in-situ hydrothermal synthesis of Fe-SSZ-13 molecular sieve

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1195655A (en) * 1997-04-04 1998-10-14 傅焕斌 Adsorption separation method for liquefied butagas isomer
US6022398A (en) * 1997-12-31 2000-02-08 Korea Institute Of Energy Research Adsorption separation and purification apparatus and process for high purity isobutane production
CN101171213A (en) * 2005-03-11 2008-04-30 环球油品公司 Processes for the isomerization of normal butane to isobutane
CN109110777A (en) * 2017-06-22 2019-01-01 中国科学院宁波材料技术与工程研究所 A kind of synthetic method of SSZ-13 molecular sieve
US20190329214A1 (en) * 2018-04-30 2019-10-31 The Regents Of The University Of Colorado, A Body Corporate Functionalization of zeolites
CN111514929A (en) * 2019-02-03 2020-08-11 周跃 Cu-SSZ-13 catalyst and H-SSZ-13 molecular sieve with double aluminum centers as well as preparation method and application thereof
CN111592008A (en) * 2020-06-12 2020-08-28 浙江浙能技术研究院有限公司 Method for in-situ hydrothermal synthesis of Fe-SSZ-13 molecular sieve

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHISHOLM N O，ET AL: "Carbon dioxide/alkane separations in a SSZ-13 membrane", 《JOURNAL OF MEMBRANE SCIENCE》 *
FENG GAO，ET AL: "Structure–activity relationships in NH3-SCR over Cu-SSZ-13 as probedby reaction kinetics and EPR studies", 《JOURNAL OF CATALYSIS》 *
HALIL KALIPCILAR，ET AL: "Synthesis and Separation Performance of SSZ-13 Zeolite Membranes on Tubular Supports", 《CHEM. MATER》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113976177A (en) * 2021-11-26 2022-01-28 华东理工大学 Eutectic solvent and preparation method and application thereof
CN113976177B (en) * 2021-11-26 2023-07-04 华东理工大学 Eutectic solvent and preparation method and application thereof
CN114307536A (en) * 2022-03-02 2022-04-12 山东神驰石化有限公司 N-butane and iso-butane separating tower in n-butane isomerization
CN114307536B (en) * 2022-03-02 2022-06-07 山东神驰石化有限公司 N-butane and iso-butane separating tower in n-butane isomerization

Also Published As

Publication number Publication date
CN113277927B (en) 2022-08-16

Similar Documents

Publication Publication Date Title
CN113277927B (en) Application of microporous molecular sieve in adsorption and separation of n-butane and isobutane
CN107638870B (en) Preparation method and application of ionic liquid and metal organic framework composite adsorbent
CA2743793C (en) Removal of ethane from natural gas at high pressure
US8552246B2 (en) Removal of carbon dioxide from paraffins
CN112645788B (en) Method for separating 2, 2-dimethylbutane and 2, 3-dimethylbutane
CN104492383A (en) Metal organic framework adsorbent as well as preparation method and application thereof
WO2021196258A1 (en) Aluminum-based metal-organic skeleton material and preparation method therefor, adsorption separation device, and method for separating hydrocarbon mixture
CN111330630B (en) Molecular sieve catalyst, preparation method thereof and liquefied petroleum gas alkylation reaction method
KR20180042144A (en) Adsorbents for the separation of olefin-paraffin mixtures including C2-C4 hydrocarbons and a separation method of olefin-paraffin gas mixtures using the same
CN109420480A (en) A kind of separation method of C 4 olefin mixture
CN110813370B (en) Method for refining aromatic hydrocarbon by utilizing microporous mesoporous core-shell structure composite molecular sieve
CN113461513B (en) Porous cobalt formate material, preparation method and application thereof, and separation method of alkane isomer mixture
CN104402663B (en) A kind of alkane impurity deep-purifying method
JPH0259808B2 (en)
CN113845127A (en) Metal ion modified Y-type molecular sieve and preparation method and application thereof
WO2022043789A1 (en) Ethylene separations using small pore zeolite ssz-45
CN108435193B (en) Reproducible organochlorine removal catalyst and preparation method thereof
WO2023124761A1 (en) Zirconium-based metal-organic framework material and preparation method therefor and use thereof, and adsorption separation device and method
US20150283535A1 (en) Method for preparing hollow carbon structure using cracking reaction of heavy hydrocarbon fraction
CN101497816B (en) Non-hydrogenation aromatization upgrading method for naphtha
CN111440045A (en) Separation method of carbon-pentaene mixture
AU2009323821A1 (en) Process for gas separation
CN105327677A (en) Adsorbent for separating bicyclo-arene in diesel oil and preparation method thereof
CN114984907B (en) Heteroatom aromatic adsorbent and preparation method thereof
CN109233927A (en) A kind of recovery process of oil field gas

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant