CN111450804A - Aluminum-based metal-organic framework material, preparation method, adsorption separation device and method for separating hydrocarbon mixture - Google Patents
Aluminum-based metal-organic framework material, preparation method, adsorption separation device and method for separating hydrocarbon mixture Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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Abstract
The invention relates to an aluminum-based metal organic framework material, a preparation method, an adsorption separation device and a method for separating a hydrocarbon mixture. The chemical formula of the aluminum-based metal-organic framework material is C54H33Al3O21It is a kind of ultra-microporous metal-organic frame material, belonging to tetragonal system. The material shows remarkable advantages in the selective separation and purification of C6 isomer, and is the first metal-organic framework material which can separate C6 single-branched chain and double-branched chain with higher efficiency at normal temperature and normal pressure.
Description
Technical Field
The invention belongs to the field of new materials and application thereof, and particularly relates to an aluminum-based metal organic framework material, a preparation method, an adsorption separation device and a method for separating a hydrocarbon mixture.
Background
Energy shortage and environmental pollution are worldwide problems facing the human society, and are also important challenges to be solved for realizing sustainable development in China. Industrial chemical separation processes (such as distillation) consume 10-15% of the world's total energy consumption each year. The development of energy-saving alternative technologies, such as adsorption separation and the like, is expected to reduce the energy consumption required by the chemical separation process, and simultaneously reduce the emission of carbon dioxide and environmental pollution. Many of these industrial separation processes are closely related to the development of national economy and society, and for example, the separation of hydrocarbons in oil refining processes is classified as one of seven chemical separation processes that can change the world. Among them, the separation of isomers of paraffins (mainly C5 and C6 paraffins) is an important process for industrially improving the octane number of gasoline. The alkane isomer is one of the constituents of gasoline. In petroleum refining processes, catalytic isomerization reactions produce a mixture of alkanes having varying degrees of branching. Generally, the more highly branched alkane isomers have higher octane numbers. Therefore, in order to achieve higher octane numbers for gasoline components and to improve gasoline antiknock performance, molecules with lower branching degrees need to be separated from the mixture of alkane isomers and returned to the catalytic isomerization treatment unit. At present, distillation technology is generally adopted in industry to separate alkane isomers, but because the boiling points of the alkane isomers are relatively close, the distillation separation process is relatively complex and the energy consumption is relatively high. Therefore, in order to reduce the energy consumption and cost required for separation, development of a more efficient, energy-saving and environment-friendly separation technology is urgently needed.
At present, the simulated moving bed technology which takes a 5A molecular sieve as an adsorbent is already used for separating alkane isomers in the oil refining process, but the application range is not wide, and particularly, domestic oil enterprises still mainly use distillation separation. Firstly, the pore volume of the 5A molecular sieve is not large enough, so that the adsorption capacity is not high enough, the saturated adsorption capacity of the molecular sieve to normal hexane is about 16 wt% at room temperature, the dynamic adsorption capacity at 150 ℃ is about 8 wt%, and the treatment capacity of the adsorption and separation device can be improved by improving the adsorption capacity of the adsorbent material, so that the efficiency of the adsorption unit is improved; more importantly, the 5A molecular sieve does not adsorb branched paraffin, so that single-branched paraffin and double-branched paraffin cannot be separated, the octane number of the isomerized oil cannot be further improved, and the practical value of the isomerized oil cannot be improved. Therefore, in order to improve the performance of the adsorption separation unit and to make the adsorption separation technology widely applicable, it is highly desirable to develop a novel adsorbent material capable of efficiently separating alkane isomers.
Metal-Organic Frameworks (MOFs) as a classThe novel crystalline porous material shows great application potential in the fields of adsorption, separation and the like due to the characteristics of high specific surface area/pore volume, surface function diversity, easy regulation and control of pore channel shape and size and the like. The characteristics of high specific surface area/pore volume, adjustable pore size and dimension height and the like of the MOFs enable the MOFs to become a potential substitute material for solving the bottleneck of adsorption and separation performance of molecular sieve materials, and thus no MOFs material can well solve the problem of efficient separation of C6 single-branched chains and double-branched chains at present. For example, Fe2(BDP)3And Zr-abtc can separate C6 single-branched alkane and double-branched alkane from the mixture thermodynamically due to different affinities to C6 single-branched chain and double-branched chain, but the selectivity is low, and the flexibility of the Ca-tcpb structure is utilized to separate the single-branched alkane and the double-branched alkane from the C6 by temperature programming, but the process is complex, high temperature is required, and a large amount of energy is consumed.
Disclosure of Invention
The invention solves the main technical problems that: the provided aluminum-based metal organic framework material is a novel crystalline porous material, and is used for solving the problems that the types of separation and adsorption materials in the existing fields of adsorption, separation and the like and the adsorption and separation performance of the separation and adsorption materials are limited.
The invention solves another technical problem that: provides a method for preparing an aluminum-based metal organic framework material to obtain a novel crystalline porous material, and solves the problems that the types of adsorption materials and the adsorption and separation performances of the adsorption materials in the existing fields of adsorption, separation and the like are limited.
The invention solves another technical problem that: provides an adsorption separation device to solve the problem that the prior art can not efficiently separate hydrocarbon mixtures.
The technical problems solved by the invention are as follows: provides a method for separating hydrocarbon mixture, which solves the problem that the prior art can not separate the hydrocarbon mixture with high efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that:
an Al-base metal-organic skeleton material with chemical formula of C54H33Al3O21Is a super-microporous metal-organic frameThe frame material belongs to the tetragonal system.
The structural formula of the aluminum-based metal-organic framework material is a crystal structural formula shown in figure 1; the structural formula of the aluminum-based metal-organic framework material is provided with a ccca space group.
The aluminum-based metal-organic framework material is prepared by taking 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid bttotb as an organic ligand and taking aluminum salt as a metal ion source through a solvothermal reaction.
In the structure of the aluminum-based metal-organic framework material, each Al ion center is coordinated with 4O atoms from carboxylate and 2O atoms from hydroxyl anions to form one-dimensional angle common AlO6An octahedral array; the one-dimensional chain is further connected with an organic ligand bttob to form a three-dimensional network structure with two square one-dimensional pore channels; the aluminum-based metal-organic framework material has two different one-dimensional pore channels.
The aluminum-based metal-organic framework material is prepared from organic ligands 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid bttotb, aluminum salt, solvent and acid, wherein the aluminum salt: organic ligand: acid: the molar ratio of the solvent is as follows: 1: (0.5-5): (50-1000): (100-1000) prepared by solvothermal reaction.
The aluminum-based metal-organic framework material is a white powder crystal; the thermal decomposition temperature of the aluminum-based metal-organic framework material is close to 500 ℃; the specific surface area of the aluminum-based metal-organic framework material is 500-800m2(ii)/g; the pore size of the aluminum-based metal-organic framework material is
The aluminum-based metal-organic framework material realizes the complete separation of C6 alkane single branch and double branch by molecular screening at normal temperature and normal pressure; the aluminum-based metal-organic framework material preferentially adsorbs straight chains of C6, then adsorbs single branches, and finally adsorbs or does not adsorb double branches.
The invention provides a method for preparing an aluminum-based metal-organic framework material, which comprises the following steps: aluminum salt, organic ligand bttotb, organic solvent and acid are mixed and dissolved in proportion, and the product obtained by solvothermal reaction is an aluminum-based metal-organic framework material.
The method further comprises the following steps:
after the solvothermal reaction is finished, washing by using an organic solvent, and carrying out suction filtration and drying to obtain the product; or
After the solvothermal reaction is finished, in order to remove reaction solvent molecules existing in the pore channel of the product structure, the reaction solvent molecules are removed by vacuum drying or vacuum drying after solvent exchange;
the aluminum salt is at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide; the acid can be at least one of formic acid, acetic acid, hydrochloric acid and benzoic acid;
the solvent thermal reaction temperature is 80-200 ℃, and the reaction time is 12-168 hours.
The invention provides an adsorption separation device, which comprises an adsorption column, wherein an adsorbent filled in the adsorption column is the aluminum-based metal-organic framework material; the adsorbent can realize regeneration.
The invention provides a method for separating a hydrocarbon mixture, which comprises the following steps: the mixed gas containing C6 alkane isomer is passed through the adsorption separation device of claim 9 at 0-200 deg.C and 0-5bar pressure, the double-branched chain of C6 preferentially penetrates the adsorption column to directly obtain the double-branched chain product with high octane number, then the single-branched chain product of C6 begins to overflow and obtain the mixed gas with the single-branched chain and the double-branched chain with high octane number, thereby realizing the effective separation of C6 branched chain and straight chain by the adsorbent.
The technical scheme at least has the following beneficial effects:
the invention designs and synthesizes a novel ultramicropore metal-organic framework material with a chemical formula of C54H33Al3O21The ultra-microporous metal-organic framework material belongs to the tetragonal system, ccca space group. The material shows remarkable advantages in the selective separation and purification of C6 isomer, and is the first material which can be used at normal temperature and pressureThe single-branched and double-branched metal-organic framework materials of C6 are separated with higher efficiency, so that high-quality high-octane gasoline blending components can be obtained. In addition, the material has strong stability and is easy for large-scale production, and the industrial production requirements can be met. The material synthesized by the invention solves the problems of low separation efficiency, high energy consumption, high pollution and the like of C6 isomer, provides a new method for preparing a high-octane gasoline blending component, and has great application prospect in the petrochemical industry.
Drawings
FIG. 1 is a crystal structure diagram of Al-bttotb of the present invention (there are A, B two different one-dimensional channels).
FIG. 2 is a conceptual diagram of selective adsorption of C6 alkane isomers by the porous aluminum-based metal-organic framework material Al-bttotb.
FIG. 3 shows the theoretical X-ray diffraction pattern of Al-bttotb, the Al-bttotb sample obtained in example 1 of the present invention, and the X-ray diffraction pattern of the sample after stability test.
FIG. 4 is a thermogravimetric plot of Al-bttotb obtained in example 1 of the present invention.
FIG. 5 is a nitrogen sorption-desorption isotherm of Al-bttotb obtained in example 1 of the present invention at 77K.
FIG. 6 is a graph showing the distribution of pore diameters of Al-bttotb obtained in example 1 of the present invention.
FIG. 7 is an adsorption isotherm of Al-bttotb obtained in example 1 of the present invention at 30 ℃ on n-hexane (nHEX), 3-methylpentane (3MP), 2-dimethylbutane (22 DMB).
FIG. 8 is a graph showing the adsorption kinetics of Al-bttotb obtained in example 1 of the present invention at 30 ℃ on nHEX, 3MP, and 22 DMB.
FIG. 9 is a multicomponent transmission curve of Al-bttotb obtained in example 1 of the present invention for a ternary mixture of nHEX, 3MP and 22 DMB.
FIG. 10 is a multicomponent transmission curve of Al-bttotb obtained in example 1 of the present invention for a five-membered mixture of nHEX, 2-methylpentane (2MP), 3MP, 22DMB and 2, 3-dimethylbutane (23 DMB).
Detailed Description
The invention designs and prepares a novel ultramicropore metal-organic framework material, namely an aluminum-based metal-organic framework material, which is a separation and adsorption material with high stability and capable of better separating a single branch chain and a double branch chain of C6 and can be applied to the petrochemical industry for preparing high-octane gasoline.
The aluminum-based metal-organic framework material of the invention takes 4,4 '- (phenyl-1, 3, 5-trioxo) -benzoic acid (4,4' - (benzone-1, 3,5-triyltris (oxy)) tribenzoic acid, abbreviated as btttotb) as an organic ligand, takes aluminum salt as a metal ion source, takes solutions of N, N-dimethylformamide (abbreviated as DMF) or N, N-diethylformamide (abbreviated as DEF) and the like as a solvent, and takes acid as a regulator; wherein, the aluminum salt: organic ligand: acid: the molar ratio of the solvent is as follows: 1: (0.5-5): (50-1000): (100-1000), a completely new structure is prepared by solvothermal reaction (reaction temperature: 80-200 ℃). Aluminum-based metal-organic framework materials (Al-bttotb), can be used to efficiently separate hydrocarbon mixtures.
An organic ligand btotb, 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid, the structural formula of which is shown as the following formula (1)
The aluminum-based metal-organic framework material (Al-btotb) is an ultra-microporous metal-organic framework material with a chemical formula of C54H33Al3O21Belongs to the tetragonal system, ccca space group. Refer to the aluminum-based metal-organic framework material Al-bttotb structure shown in fig. 1. In the Al-bttotb material structure, each Al ion center is coordinated with 4O atoms from carboxylate (bttotb) and 2O atoms from hydroxyl anions to form one-dimensional angle common AlO6An octahedral array. The one-dimensional chain is further connected with an organic ligand bttob to form a three-dimensional network structure with two square one-dimensional pore channels. The aluminum-based metal-organic framework material Al-bttotb has A, B two different one-dimensional pore channels. The size of the one-dimensional pore channel structure is about
The Al-bttotb used for preparing the aluminum-based metal-organic framework material has the advantages of low price of required raw materials, simple preparation process and easy large-scale production, and can meet the requirement of industrialized production.
The Al-based metal-organic framework material Al-bttotb has strong stability and has good stability in high temperature, water vapor environment and water immersion.
The aluminum-based metal-organic framework material Al-bttotb can realize high-selectivity separation on a single branch and a double branch of C6 through molecular screening, shows remarkable advantages in selective separation and purification of C6 isomer, and can separate the single branch and the double branch of C6 at high efficiency at normal temperature and pressure. The aluminum-based metal-organic framework material Al-bttotb is applied to the petrochemical industry to prepare high-octane gasoline, and high-quality high-octane gasoline blending components can be obtained.
The aluminum-based metal-organic framework material synthesized by the method solves the problems of low separation efficiency, high energy consumption, high pollution and the like of C6 isomer, provides a new method for preparing a high-octane gasoline blending component, and has great application prospect in the petrochemical industry.
The method for preparing the ultra-microporous aluminum-based metal-organic framework material mainly comprises the following steps: mixing aluminum salt, organic ligand btotb, organic solvent and acid in proportion, dissolving by ultrasonic or stirring, and putting into a reaction kettle or a glass bottle or other closed containers for solvothermal reaction. After cooling, filtration gave white powdery crystals.
In some embodiments, after the solvothermal reaction is finished, the organic solvent can be adopted for washing for multiple times, and the required product can be obtained after suction filtration and drying.
Preferably, in order to remove the reaction solvent molecules existing in the pore channels of the product structure, the reaction solvent molecules can be removed by vacuum drying or solvent exchange and then vacuum drying, so as to obtain the ultra-microporous metal-organic framework material Al-btttotb.
Wherein the aluminum salt is at least one of aluminum nitrate, aluminum chloride and aluminum sulfate.
The solvent is at least one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA) and N, N-Diethylformamide (DEF).
The acid may be at least one of formic acid, acetic acid, hydrochloric acid, and benzoic acid.
The solvent thermal reaction temperature is 80-200 ℃, and the reaction time is 12-168 hours.
The materials are sufficiently dissolved and mixed by adjusting appropriate ultrasonic wave or stirring, and the ultrasonic wave or stirring condition is not particularly limited.
The solution for organic solvent washing or solvent exchange may be at least one of methanol, dichloromethane, and ethanol.
The vacuum drying temperature is 80-250 deg.C, and the drying time is 6-24 hr.
The ultra-microporous aluminum-based metal-organic framework material prepared by the method is pure, free of impurities and regular in shape, can be used as an adsorbent material for separating hydrocarbon mixtures, and can be used for completely screening direct-connection, single-branch and double-branch isomers of C6 alkane.
The invention provides a molecular sieve made of the aluminum-based metal-organic framework material, which is used as an adsorbent and can efficiently separate hydrocarbon mixed gas, in particular to the mixed gas containing direct-connection, single-branch and double-branch isomers of C6 alkane. Referring to the conceptual diagram shown in FIG. 2: the prepared ultra-microporous aluminum-based metal organic framework material Al-bttotbb can selectively adsorb straight chain and single-branched chain components of C6 alkane isomers and does not adsorb double-branched chain components, so that the straight chain, single-branched chain and double-branched chain components of C6 alkane isomers can be separated.
The aluminum-based metal-organic framework material is used as an adsorbent for separating gasoline in the petroleum industry, and direct-connection, single-branched chain and double-branched chain isomers of C6 alkane are subjected to adsorption separation, so that high-quality gasoline blending components with high octane number are obtained.
The invention also provides a method for separating hydrocarbon mixtures, in particular a method for separating direct-connection, single-branch and double-branch isomers of C6 alkane, wherein the aluminum-based metal-organic framework material is an adsorbent and is used for adsorbing and separating the direct-connection, single-branch and double-branch isomers of C6 alkane so as to obtain high-quality gasoline blending components with higher octane number.
The method for separating the hydrocarbon mixture is realized by an adsorption separation device, and mainly adopts any one of fluidized bed adsorption, moving bed adsorption and fixed bed adsorption. Moving bed adsorption is preferred. The adsorption separation device comprises an adsorption column, and an adsorbent filled in the adsorption column is the aluminum-based metal-organic framework material. Preferably, the separation temperature of the adsorption column is 0-200 deg.C, and the total pressure of the separated mixed gas is 0-5 bar. Preferably, the temperature of adsorption separation is 20-150 deg.C, and the total pressure of the mixed gas is 0.05-0.5 bar.
The method for separating the hydrocarbon mixed gas comprises the following steps:
the mixed gas of a straight chain (normal hexane) containing C6 alkane isomer and a single branched chain (2-methylpentane, 3-methylpentane) double branched chain (2, 2-dimethylbutane, 2, 3-dimethylbutane) passes through a fixed bed adsorption column filled with an adsorbent (the prepared ultra-microporous aluminum-based metal-organic framework material) at a certain temperature and pressure at a certain flow rate, and the normal hexane has strong interaction with the pore channels of the adsorbent, the single branched chain and the pore channels of the adsorbent are weak, and the kinetic size of the double branched chain is larger than the size of the pore channels, so that the adsorbent preferentially adsorbs the straight chain of C6, and then adsorbs the single branched chain, and does not adsorb the double branched chain, namely the double branched chain preferentially penetrates through the fixed bed, and therefore, the double branched chain product with high purity and high octane number can be directly obtained. Then, the single-chain product also begins to overflow, and a mixed gas of single-chain and double-chain with higher octane number can be obtained, so that the effective separation of C6 branched chain and straight chain by the adsorbent is realized.
The linear component of C6 has strong action force with the adsorbent, so it can be enriched in the fixed bed, after it is penetrated, the linear component adsorbed in the adsorbent can be eluted by heating, vacuum treatment, inert gas purging or various desorption methods, so it can obtain high-purity linear C6 gas.
The separation temperature is 0-200 ℃, and the total pressure of the mixed gas is 0-5 bar. Preferably, the temperature of adsorption separation is 20-150 deg.C, and the total pressure of the mixed gas is 0.05-0.5 bar.
The mixed gas to be separated is not limited to only containing C6 alkane isomers, and may also contain other gases such as oxygen, nitrogen, helium, carbon dioxide, water vapor, methane and the like.
The adsorbent can be regenerated only by desorption treatment.
The aluminum-based metal-organic framework material has the advantages of low price of raw materials, mild conditions, simple synthesis process, pure product and large-scale preparation. The aluminum-based metal-organic framework material has excellent stability, the decomposition temperature is close to 500 ℃, and the aluminum-based metal-organic framework material can still keep the structural integrity and has no obvious reduction in performance adsorption separation no matter being exposed to the high temperature of 180 ℃ for 7 days, the air with the relative humidity reaching 90 percent for 7 days or being placed in the water of 80 ℃ for 7 days.
The invention is the only one metal-organic framework material which can realize the complete separation of C6 alkane single branch chain and double branch chain by molecular sieving at normal temperature and normal pressure, the separation method provided by the invention can obtain the C6 double branch chain component with the purity of 99.5 percent and the C6 straight chain component with the purity of 99.5 percent at most, and can obtain the gasoline blending component with the octane number of more than 95.
Compared with the conventional low-temperature rectification method, the separation method provided by the invention has the advantages of low cost, energy conservation, environmental protection, simplicity in operation and the like, and is expected to bring improvement on quality and economic benefits for petrochemical enterprises in preparation of high-octane gasoline blending components.
The following is a non-limiting illustration of the present invention for the preparation of aluminum-based metal-organic framework materials and its application to the separation of hydrocarbon mixtures.
Example 1
1mmol of aluminum nitrate nonahydrate and 0.4mmol of 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid are added into a mixed solution consisting of 10m L formic acid and 20m L N, N-dimethylformamide, stirred for 30min, transferred into a 100m L reaction kettle, then placed into an oven at 150 ℃ for reaction for 72 hours, cooled and filtered to obtain white powder crystals.
In order to remove the solvent existing in the crystal pore canal, the material obtained by filtration is soaked in a methanol solution for 48 hours, the N, N-dimethylformamide solvent in the material pore canal is fully replaced by methanol, then the material after solvent exchange is filtered, and vacuum degassing is carried out for 12 hours at 120 ℃ to obtain the aluminum-based metal-organic framework material without the solvent, and the aluminum-based metal-organic framework material can be used as a novel adsorbent.
In order to test the specific surface area and pore size distribution of the above synthesized adsorbent, the above degassed adsorbent material (aluminum-based metal-organic framework material) was subjected to a nitrogen adsorption-desorption isotherm test at 77K. Referring to FIG. 5, the nitrogen adsorption-desorption isotherm of Al-btotb obtained in this example at 77K was tested to show that the specific surface area of the material is 500-800m2/g, and the adsorption capacity in the low-pressure region sharply increases and then tends to be balanced, which indicates that the material is a microporous material.
Referring to FIG. 6, the pore size distribution of Al-bttotb obtained in this example is shown, and the pore size of Al-bttotb obtained in this example is about
Referring to FIG. 3, an X-ray diffraction pattern of the Al-bttotb structure and the Al-bttotb sample obtained in this example and the X-ray diffraction pattern of the sample subjected to the stability test are shown. In order to test the stability of the synthesized adsorbent, the prepared adsorbent is respectively placed in an oven at 180 ℃, water at 80 ℃ and air with the humidity of 90% at room temperature, and after the adsorbent is placed for 7 days, an X-ray diffraction analysis test is carried out, and test results show that the three processed materials still keep complete crystal structures, which shows that the adsorbent has good stability.
The thermogravimetric test of the Al-bttotb obtained in this example and the sample after the solvent exchange is performed, please refer to FIG. 4, and it can be seen from the thermogravimetric curve shown in FIG. 4 that the material can resist a high temperature of 500 ℃ and has excellent thermal stability. The first weight loss platform after solvent exchange was cut off at 50 ℃ and the Al-bttotb weight loss platform without solvent exchange was cut off at about 170 ℃, which indicates that the material after solvent exchange can lose solvent molecules at lower temperature.
Referring to fig. 7, in order to test the adsorption separation performance of the above-described synthetic adsorbent of this example, Al-bttotb obtained in example 1 was used as an adsorbent, and the adsorbent subjected to desorption treatment was subjected to single-component adsorption isotherms of nHEX, 3MP, and 22DMB, respectively, in which the adsorption amount of nHEX was 151mg/g, the adsorption amount of 3MP was 94mg/g, and 22DMB had almost no adsorption, the selectivity of nHEX/22DMB was 63, and the selectivity of 3MP/22DMB was 44 under a test environment of a temperature of 30 ℃ and a pressure of 1 bar.
Referring to fig. 8, when Al-bttotb obtained in example 1 was used as an adsorbent, the adsorption kinetics curves of nHEX, 3MP, and 22DMB were tested at 30 ℃, and nHEX adsorption speed was very fast, and the adsorption amount reached 21mg/g at 25 s; the adsorption speed of 3MP is faster, the adsorption amount reaches 14mg/g at 100s, and 22DMB does not adsorb.
Referring to fig. 9, in order to test the actual separation effect of the adsorbent on the C6 alkane isomer, Al-btttotb obtained in example 1 was used as the adsorbent, and a multicomponent permeation experiment of a trihydric mixture of nHEX, 3MP and 22DMB was performed on the adsorbent subjected to desorption treatment, in this experiment, a trihydric mixture of nHEX, 3MP and 22DMB of equal molar weight was passed through an adsorption column filled with the adsorbent by helium gas at a test temperature of 30 ℃, a pressure of 1bar, and a mixed gas flow rate of 1m L/min, and it was tested that 22DMB was permeated at the beginning, 3MP was permeated at 23 minutes, and nHEX was permeated only at 100 minutes, which effectively separated nHEX, 3MP and 22DMB, and 22DMB having a purity of more than 99.5% was obtained, and a gasoline blending component having an octane number of more than 95 was obtained.
Referring to fig. 10, in order to further aggravate the separation effect of the adsorbent material on the C6 alkane isomer, Al-bttotbb obtained in example 1 was used as an adsorbent, and a multicomponent permeation experiment of a five-membered mixed gas of nHEX, 2MP (2-methylpentane), 3MP, 22DMB, 23DMB (2, 3-dimethylbutane) was performed on the adsorbent subjected to desorption treatment, in this experiment, a five-membered mixture of nHEX, 2MP, 3MP, 22DMB, 23DMB of medium moles was subjected to helium gas as an adsorption column filled with the adsorbent, the test temperature was 30 ℃, the pressure was 1bar, and the mixed gas flow rate was 1m L/min, and the beginning of the test was that 22DMB was permeated at one minute, 23DMB permeation was initiated at 4 minutes, 2MP and 3MP were permeated at 15 minutes, and only at 106 minutes, nHEX permeation was initiated, and the material was capable of effectively separating nHEX, 2MP, 3MP, 22 octane number, 23 octane number, and 23 was capable of obtaining a high-purity gasoline of more than 0.99% and capable of obtaining a high-purity gasoline.
Example 2
1.6mmol of aluminum nitrate nonahydrate and 0.8mmol of 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid are added into a mixed solution consisting of 3m L formic acid and 30m L N, N-dimethylformamide, the mixture is subjected to ultrasonic treatment for 30min, and then the mixture is transferred into a 50m L glass bottle, the bottle cap is screwed, the glass bottle is placed into an oven at 120 ℃ for reaction for 50 hours, and white powder crystals are obtained after cooling and filtering.
And further carrying out vacuum degassing on the aluminum-based metal-organic framework material Al-bttotb prepared in the process at 180 ℃ for 10 hours to obtain the aluminum-based metal-organic framework material Al-bttotb with the solvent removed. The Al-based metal-organic framework material Al-bttotb prepared by the embodiment can be used as a novel adsorption material and an adsorbent. In order to test the adsorption separation performance of the adsorbent synthesized in this example, single-component adsorption isotherms of nHEX, 3MP, and 22DMB were respectively tested using the desorption-treated adsorbent Al-bttottb of this example, and the adsorption amount of nHEX was 142mg/g, the adsorption amount of 3MP was 82mg/g, and 22DMB hardly adsorbs under a test environment at a temperature of 50 ℃ and a pressure of 0.5 bar. The selectivity of nHEX/22DMB is 60, and the selectivity of 3MP/22DMB is 42.
In order to test the actual separation effect of the adsorbent on C6 alkane isomers, a multicomponent penetration experiment of a ternary mixture gas of nHEX, 3MP and 22DMB is carried out by using the desorbed adsorbent Al-btttotb of the embodiment, in the experiment, the ternary mixture of medium-molar nHEX, 3MP and 22DMB is penetrated by helium gas as an adsorption column filled with the adsorbent, the test temperature is 50 ℃, the pressure is 1bar, and the flow rate of the mixed gas is 0.5m L/min.
Example 3
4mmol of aluminum nitrate nonahydrate and 1.5mmol of 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid are added into a mixed solution consisting of 35m L formic acid and 80m L N, N-dimethylformamide, stirred for 30min, transferred into a 250m L reaction kettle, placed into an oven at 160 ℃ for reaction for 50 hours, cooled and filtered to obtain white powder crystals.
The Al-bttotb material prepared by the above process is further degassed at 130 ℃ in vacuum for 15 hours to obtain a solvent-removed metal-organic framework material Al-bttotb. The Al-based metal-organic framework material Al-bttotb prepared by the embodiment can be used as a novel adsorption material and an adsorbent. In order to test the adsorption separation performance of the synthetic adsorbent Al-bttotbb, single-component adsorption isotherms of nHEX, 3MP and 22DMB were respectively tested using the adsorbent Al-bttotbb subjected to desorption treatment, and the adsorption amount of nHEX was 162mg/g, the adsorption amount of 3MP was 101mg/g and 22DMB hardly adsorbed in a test environment at a temperature of 25 ℃ and a pressure of 1 bar. The selectivity of nHEX/22DMB is 58, and the selectivity of 3MP/22DMB is 38.
In order to test the actual separation effect of the adsorbent Al-btttotb on C6 alkane isomers, a multicomponent penetration experiment of a ternary mixed gas of nHEX, 3MP and 22DMB is carried out by using the desorbed adsorbent Al-btttotb, in the experiment, the ternary mixture of medium-molar nHEX, 3MP and 22DMB is penetrated by helium gas as an adsorption column filled with the adsorbent, the test temperature is 50 ℃, the pressure is 1bar, and the flow rate of the mixed gas is 0.5m L/min.
Example 4
0.7mmol of aluminum nitrate nonahydrate and 0.4mmol of 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid are added into a mixed solution consisting of 1.6m L formic acid and 14m L N, N-dimethylformamide, stirred for 60min, transferred into a reaction kettle of 25m L, then the reaction kettle is put into an oven at 130 ℃ for reaction for 60 hours, cooled and filtered to obtain white powder crystals.
The material Al-bttotb prepared in the above process is further degassed at 160 ℃ for 9 hours in vacuum to obtain the metal-organic framework material Al-bttotb with the solvent removed. The Al-based metal-organic framework material Al-bttotb prepared by the embodiment can be used as a novel adsorption material and an adsorbent. In order to test the adsorption separation performance of the adsorbent Al-bttotbb synthesized in this example, the adsorbent Al-bttotbb subjected to the desorption treatment described above was used to perform a single-component adsorption isotherm test of nHEX and 22DMB, respectively, wherein the adsorption amount of nHEX was 122mg/g, and 22DMB hardly adsorbs under a test environment at a temperature of 80 ℃ and a pressure of 1 bar. The selectivity of nHEX/22DMB was 57.
In order to test the actual separation effect of the adsorbent Al-btttotb on C6 alkane isomers, a multicomponent penetration experiment of nHEX and 22DMB binary mixed gas is carried out by using the desorbed adsorbent Al-btttotb, in the experiment, the binary mixture of medium molar nHEX and 22DMB is taken as helium to pass through an adsorption column filled with the adsorbent, the test temperature is 80 ℃, the test pressure is 1bar, the mixed gas flow rate is 1.5m L/min, through the test, 22DMB penetrates at the beginning, and nHEX penetrates only at 120 minutes.
Example 5
0.25mmol of aluminum nitrate nonahydrate and 0.1mmol of 4,4' - (phenyl-1, 3, 5-trioxo) -benzoic acid are added into a mixed solution consisting of 2m L formic acid and 5m L N, N-dimethylformamide, the mixture is transferred into a reaction kettle of 20m L after ultrasonic dispersion for 45min, and then the reaction kettle is put into an oven at 140 ℃ for reaction for 80 hours, and white powder crystals are obtained after cooling and filtration.
The material Al-bttotb prepared by the process takes methanol as a solvent, and is subjected to solvent exchange and vacuum degassing at 120 ℃ for 8 hours to obtain the metal-organic framework material Al-bttotb with the solvent removed. The Al-based metal-organic framework material Al-bttotb prepared by the embodiment can be used as a novel adsorption material and an adsorbent. In order to test the adsorption separation performance of the adsorbent Al-bttotbb synthesized and placed in the present example, the single-component adsorption isotherms of 3MP and 22DMB were respectively tested using the above-described desorbed adsorbent Al-bttotbb, and the adsorption amount of 3MP was 108mg/g, while the adsorption amount of 22DMB was almost no, under the test environment of 0 ℃ temperature and 1bar pressure. The selectivity of 3MP/22DMB is 46.
In order to test the actual separation effect of the adsorbent Al-btttotb on C6 alkane isomers, a multicomponent penetration experiment of ternary mixed gas of 3MP and 22DMB is carried out by using the desorbed adsorbent Al-btttotb in the embodiment, in the experiment, the ternary mixture of medium-molar nHEX, 3MP and 22DMB is taken as helium to pass through an adsorption column filled with the adsorbent, the test temperature is 0 ℃, the pressure is 1bar, and the flow rate of the mixed gas is 0.35m L/min.
While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (10)
1. An aluminum-based metal-organic framework material, characterized in that the aluminum-based metal-organic framework material has a chemical formula of C54H33Al3O21It is a kind of ultra-microporous metal-organic frame material, belonging to tetragonal system.
2. The aluminum-based metal-organic framework material of claim 1, wherein the aluminum-based metal-organic framework material has a crystal structure as shown in fig. 1; the structural formula of the aluminum-based metal-organic framework material is provided with a ccca space group.
3. The aluminum-based metal-organic framework material of claim 1, wherein the aluminum-based metal-organic framework material is a metal-organic framework material prepared by solvothermal reaction using 4,4',4 "- (phenyl-1, 3, 5-trioxo) -benzoic acid bttotb as an organic ligand and aluminum salt as a metal ion source.
4. The aluminum-based metal-organic framework material of claim 3, wherein the aluminum-based metal-organic framework material has a structure in which each Al ion center is coordinated with 4O atoms from the carboxylate and 2O atoms from the hydroxyl anion to form a one-dimensional angular common AlO6An octahedral array; the one-dimensional chain is further connected with an organic ligand bttob to form a three-dimensional network structure with two square one-dimensional pore channels; the aluminum-based metal-organic framework material has two different one-dimensional pore channels.
5. The aluminum-based metal-organic framework material of claim 3, wherein the aluminum-based metal-organic framework material is prepared from the organic ligands 4,4',4 "- (phenyl-1, 3, 5-trioxo) -benzoic acid bttotb, aluminum salts, solvents, acids, in the form of aluminum salts: organic ligand: acid: the molar ratio of the solvent is as follows: 1: (0.5-5): (50-1000): (100-1000) prepared by solvothermal reaction.
6. The aluminum-based metal-organic framework material according to any of claims 1 to 5, wherein the aluminum-based metal-organic framework material is a white powder crystal; the thermal decomposition temperature of the aluminum-based metal-organic framework material is close to 500 ℃; the specific surface area of the aluminum-based metal-organic framework material is 500-800m2(ii)/g; the pore size of the aluminum-based metal-organic framework material is
The aluminum-based metal-organic framework material realizes the complete separation of C6 alkane single branch and double branch by molecular screening at normal temperature and normal pressure; the aluminum-based metal-organic framework material preferentially adsorbs straight chains of C6, then adsorbs single branches, and finally adsorbs or does not adsorb double branches.
7. A method for preparing an aluminium based metal-organic framework material according to any of claims 1 to 6, comprising the steps of: aluminum salt, organic ligand bttotb, organic solvent and acid are mixed and dissolved in proportion, and the product obtained by solvothermal reaction is an aluminum-based metal-organic framework material.
8. The method of claim 7,
the method further comprises the following steps:
after the solvothermal reaction is finished, washing by using an organic solvent, and carrying out suction filtration and drying to obtain the product; or
After the solvothermal reaction is finished, in order to remove reaction solvent molecules existing in the pore channel of the product structure, the reaction solvent molecules are removed by vacuum drying or vacuum drying after solvent exchange;
the aluminum salt is at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide;
the acid can be at least one of formic acid, acetic acid, hydrochloric acid and benzoic acid;
the solvent thermal reaction temperature is 80-200 ℃, and the reaction time is 12-168 hours.
9. An adsorption separation device, which is characterized in that the adsorption separation device comprises an adsorption column, and an adsorbent filled in the adsorption column is the aluminum-based metal-organic framework material as claimed in any one of claims 1 to 6; the adsorbent can realize regeneration.
10. A method of separating a mixture of hydrocarbons comprising the steps of: the mixed gas containing C6 alkane isomer is passed through the adsorption separation device of claim 9 at 0-200 deg.C and 0-5bar pressure, the double-branched chain of C6 preferentially penetrates the adsorption column to directly obtain the double-branched chain product with high octane number, then the single-branched chain product of C6 begins to overflow and obtain the mixed gas with the single-branched chain and the double-branched chain with high octane number, thereby realizing the effective separation of C6 branched chain and straight chain by the adsorbent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004115A (en) * | 2021-02-03 | 2021-06-22 | 浙江大学 | Method for separating mixed hexane isomers |
| CN114058024A (en) * | 2021-11-04 | 2022-02-18 | 山东能源集团有限公司 | Ultramicropore metal-organic framework material and preparation method thereof |
| CN114870820A (en) * | 2022-05-20 | 2022-08-09 | 浙江大学 | Metal organic framework material suitable for adsorption separation of xenon and krypton and preparation and application thereof |
| CN115554986A (en) * | 2022-09-20 | 2023-01-03 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
| WO2023124761A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Zirconium-based metal-organic framework material and preparation method therefor and use thereof, and adsorption separation device and method |
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| CN115044050B (en) * | 2022-05-25 | 2023-03-21 | 华南理工大学 | Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111262A (en) * | 2013-01-31 | 2013-05-22 | 北京大学 | Porous material of metal-organic framework and preparation method of material |
| CN105131025A (en) * | 2015-07-24 | 2015-12-09 | 郑州轻工业学院 | Micro-pore aluminum-based metal-organic framework material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005054523A1 (en) * | 2005-11-14 | 2007-05-16 | Basf Ag | Porous organometallic framework containing another polymer |
| US9610560B2 (en) * | 2014-02-03 | 2017-04-04 | Northwestern University | Metal-organic framework compounds with ligand-functionalized metal nodes |
| CN104892518B (en) * | 2014-03-05 | 2018-04-27 | 中国科学院大连化学物理研究所 | The preparation method and applications of porous nano metal organic framework materials |
| CN104497032B (en) * | 2014-11-21 | 2016-03-16 | 中国石油大学(华东) | A kind of nanoscale aluminium based metal-organic framework material and preparation method thereof |
-
2020
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105131025A (en) * | 2015-07-24 | 2015-12-09 | 郑州轻工业学院 | Micro-pore aluminum-based metal-organic framework material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004115A (en) * | 2021-02-03 | 2021-06-22 | 浙江大学 | Method for separating mixed hexane isomers |
| CN113004115B (en) * | 2021-02-03 | 2022-05-17 | 浙江大学 | Method for separating mixed hexane isomers |
| CN114058024A (en) * | 2021-11-04 | 2022-02-18 | 山东能源集团有限公司 | Ultramicropore metal-organic framework material and preparation method thereof |
| WO2023124761A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Zirconium-based metal-organic framework material and preparation method therefor and use thereof, and adsorption separation device and method |
| CN114870820A (en) * | 2022-05-20 | 2022-08-09 | 浙江大学 | Metal organic framework material suitable for adsorption separation of xenon and krypton and preparation and application thereof |
| CN115554986A (en) * | 2022-09-20 | 2023-01-03 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
| CN115554986B (en) * | 2022-09-20 | 2023-08-25 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
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