CN114085386B - Large-scale synthesis method of low-cost Cu (BDC) and application of large-scale synthesis method in ethane-ethylene separation - Google Patents

Large-scale synthesis method of low-cost Cu (BDC) and application of large-scale synthesis method in ethane-ethylene separation Download PDF

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CN114085386B
CN114085386B CN202111491388.6A CN202111491388A CN114085386B CN 114085386 B CN114085386 B CN 114085386B CN 202111491388 A CN202111491388 A CN 202111491388A CN 114085386 B CN114085386 B CN 114085386B
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ethane
bdc
ethylene
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adsorption
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CN114085386A (en
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陈琳
孔五忠
贺朝辉
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Henan Chenglongyi New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G83/008—Supramolecular polymers
    • 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
    • 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
    • B01J20/22—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
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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 physical properties
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    • 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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    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to the field of gas separation, in particular to a large-scale synthesis method of low-cost Cu (BDC) and application thereof in high-efficiency separation of ethane and ethylene, and aims to solve the problems of complex synthesis and high cost of the traditional ethane selective adsorbent. The method comprises the following steps: mixing copper nitrate trihydrate, terephthalic acid and DMF, and stirring to obtain a hydrothermal precursor; sealing the mixed solution, and then placing the sealed mixed solution in a baking oven at 120 ℃ for hydrothermal reaction; after the reaction is finished, filtering, washing and drying are carried out, so that Cu (BDC) materials can be prepared in batches. The synthesis method provided by the invention reduces the production cost, enlarges the synthesis scale, and has high reaction yield which can reach more than 80%; the adsorbent prepared by the method has strong adsorption force and high selectivity to ethane and good stability, can realize the high-efficiency separation of ethane and ethylene, can generate polymer grade ethylene product gas through one-step adsorption separation, and is suitable for industrial production.

Description

Large-scale synthesis method of low-cost Cu (BDC) and application of large-scale synthesis method in ethane-ethylene separation
Technical Field
The invention relates to the field of gas separation, in particular to a large-scale synthesis method of low-cost Cu (BDC) and application thereof in high-efficiency separation of ethane and ethylene.
Background
Ethylene (C) 2 H 4 ) Is one of the largest chemical products in the world, and is widely used for manufacturing polymers such as polyethylene, polyvinyl chloride, polystyrene and other organic chemicals. Steam cracking and ethane dehydrogenation are the main processes for the production of ethylene, in which ethane (C) 2 H 6 ) And (5) impurities. However, the separation of olefins and paraffins is considered one of the seven world-changing chemical separations, since the total energy used for the separation of ethylene and propylene per year represents more than 0.3% of the global energy consumption. The traditional cryogenic rectification method can have the significant problem of overlarge energy consumption while maintaining higher separation efficiency. If the ethylene is separated from the ethane component with low concentration in an adsorption separation mode, the ethylene can be efficiently separated and enriched, and the polymerization grade ethylene product gas with higher purity can be obtained in one step, which has great significance. After a few decades of research by researchers, several tens of ethane selective adsorbents having adsorption effect on ethane have been reported. However, although existing materials can achieve separation C 2 H 6 And C 2 H 4 But the preparation process is complex, the ligand cost is high, the structural stability is poor, and the possibility of industrial application is limited. On the other hand, the adsorption capacity and selectivity of the adsorbent material are often not compatible. Therefore, there is an urgent need to develop a C 2 H 6 High adsorption capacity, good selectivity, low cost and simple synthesis of C 2 H 6 A selective adsorbent.
As far as the existing MOF adsorption materials are concerned, different MOF materials can be used for gas adsorption separation, but the overall research is biased to the adsorption effect level, and the MOF production method suitable for industrial application is not considered. While the current separation materials are somewhat specific to CO 2 、H 2 Is remarkable in separation effect, as disclosed in CN111004398A, the microporous Cu-MOF material selectively separates CO 2 /N 2 And CO 2 /CH 4 The ligand of the catalyst is 5- (triazole-1-yl) isophthalic acid (H2 TIPA), the preparation cost is high, the raw materials required for the mass production are complex, and the material is not suitable for C 2 H 6 / C 2 H 4 A system. And at C 2 H 6 / C 2 H 4 The MOF material used in gas separation has complex preparation method and expensive raw materials, for example, CN112657471A discloses a preparation method of a low-concentration acetylene efficient trapping agent, wherein the trapping agent is Zn2 (bpy) (btec) metal organic framework material, and the ligands are pyromellitic dianhydride and 4,4' -bipyridine, so that the MOF material has good effect on separating vinyl acetylene, but the raw materials have high production cost and complex process. To obtain C suitable for industrial application 2 H 6 / C 2 H 4 The MOF material for gas separation and better adsorption separation performance are obtained, and different MOF separation materials and preparation methods are explored.
Ligands are one of the most expensive materials in MOFs production, which can be up to 40% or more of the total production cost (including materials, equipment, energy sources, and labor used in each step of synthesis, filtration, and drying). Currently, relatively inexpensive ligands for MOFs are terephthalic acid (BDC), isophthalic acid, fumaric acid, etc., wherein BDC is a common commodity organic chemical that can cost as low as $ 750 per ton (< 5000 yuan/ton), is very competitive as an inexpensive ligand for MOFs, and further BDC has many advantages of low toxicity, availability, mature production process, etc. In the prior art, CN112002938A discloses a composite solid electrolyte membrane based on Cu (BDC) MOF multi-stage structure and a preparation method thereof, which are used for researching electrical properties without involving gas separation, and the preparation method thereof has high energy consumption and high cost, and the MOF prepared on the non-woven fabric has compact distribution, which can affect the gas adsorption separation performance of the MOF, and the preparation method is not suitable for preparing the MOF material for gas separation.
Therefore, the invention prepares the catalyst with good adsorption performance and selectivity based on cheap ligand material and metal, is suitable for industrial application separation, saves a large amount of energy and simultaneously saves the production cost, and is C 2 H 6 /C 2 H 4 The separation provides a new production process.
Disclosure of Invention
The invention prepares Cu (BDC) in batches by adjusting the dosage of reaction raw materials and solvents, in particular to a large-scale synthesis method of low-cost Cu (BDC) and application thereof in high-efficiency separation of ethane and ethylene.
The invention is realized by the following technical scheme: a large-scale synthesis method of low-cost Cu (BDC), which comprises the following steps:
mixing a copper source, terephthalic acid and DMF, and stirring until the mixture is clear to obtain a mixed solution; transferring the obtained hydrothermal precursor into a glass bottle, placing the glass bottle into a constant-temperature drying oven, performing hydrothermal reaction, filtering, washing and drying a sample obtained by the reaction, and obtaining the Cu (BDC) (DMF) material.
Further, in the step 1, the molar amounts of the copper source and terephthalic acid are equal;
further, the molar ratio of DMF to terephthalic acid is 1:20-40.
Further, the reaction temperature is controlled to be 110-130 ℃ and the reaction time is controlled to be 24-48 h.
Further, the copper source is copper acetate or copper nitrate.
As a further improvement of the technical scheme of the synthesis method, cu (BDC) can be prepared in batches by simple stirring and mixing, heating reaction and filtering and drying.
As a further improvement of the technical scheme of the synthesis method, the metal salt and the ligand used in the synthesis process are low in price, and the metal salt and the ligand are one of the materials with the lowest cost in all ethane-selective MOFs materials reported at present.
The invention further provides an application of Cu (BDC) prepared by the large-scale synthesis method of low-cost Cu (BDC) in separating ethane and ethylene gas systems, wherein the application comprises the following steps of: introducing ethane-ethylene mixed gas into an adsorption column filled with Cu (BDC) material, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out dynamic adsorption penetration experiment under certain temperature and pressure; the concentrations of ethane and ethylene were monitored in real time by gas chromatography at the outlet of the adsorption column.
As a further improvement of the high-efficiency separation method, the volume fraction of ethane in the mixed gas is 0-50%, and the volume fraction of ethane is not zero.
As a further improvement of the efficient separation method, the sample filled in the adsorption column is 1-2 g, the flow rate of the ethane-ethylene mixed gas entering the adsorption column is 0-5 mL/min, and when ethane is adsorbed on the adsorbent, the adsorption temperature is 0-25 ℃, and the pressure is 1 bar or more.
As a further improvement of the efficient separation method, the Cu (BDC) can realize the efficient separation of ethane and ethylene, and can generate polymerization grade ethylene product gas through one-step adsorption separation>99.99 percent) and the yield of the high-purity ethylene obtained by one-time penetration experiment is 15-20 cm 3 /g。
By adopting the technical scheme, the invention has the following beneficial effects:
1) According to the large-scale synthesis method of low-cost Cu (BDC), the used raw materials are low in cost and easy to obtain, and compared with other BTEC and other raw materials, terephthalic acid ligand is one of the ethane-selective MOFs with lower cost at present. By adopting a hydrothermal method, through simple stirring and mixing, heating reaction, filtering and drying, the reaction yield is high and can reach more than 80%, and the industrial synthesis of MOFs materials is hopeful to be realized.
2) Compared with the traditional adsorption material (molecular sieve, carbon material), the ethane selective adsorbent prepared by the invention has stronger adsorption force to ethane by a unique stereo ring structure, so that the ethane selective adsorbent has high ethane adsorption capacity and ethane-ethylene separation selectivity. The adsorption BET amount can reach 581m 2 And/g, the structure endows the adsorbent with better structural stability and thermal stability, is easy to desorb after adsorption, has strong reusability and can be better suitable for industrialization.
3) The Cu (BDC) prepared by the invention can realize the high-efficiency separation of ethane and ethylene, and can generate the polymerization grade ethylene product gas through one-step adsorption separation>99.99 percent) and the yield of the high-purity ethylene obtained by one-time penetration experiment is 15-20 cm 3 /g。
Drawings
FIG. 1 is a schematic diagram showing the synthesis of Cu (BDC) obtained in example 1;
FIG. 2 is a schematic diagram of one-dimensional channels of Cu (BDC) obtained in example 1;
FIG. 3 is an XRD contrast pattern of Cu (BDC) obtained in example 1 and a simulated peak;
FIG. 4 is an SEM image of Cu (BDC) obtained in example 1;
FIG. 5 is a graph showing the adsorption and desorption of nitrogen at 77K for Cu (BDC) obtained in example 1;
FIG. 6 is an adsorption curve of Cu (BDC) to ethane ethylene at 298K obtained in example 1;
FIG. 7 is a diagram of an adsorption column and a penetration test apparatus;
FIG. 8 is a graph showing the penetration of Cu (BDC) obtained in example 1 into ethane-ethylene mixtures of different proportions at room temperature; a is ethane: ethylene=1:1 (v/v), b is ethane: ethylene=1:9 (v/v);
FIG. 9 is an XRD pattern of Cu (BDC) obtained in example 1 after being treated under different conditions;
FIG. 10 shows the adsorption isotherms of Cu (BDC) obtained in example 1 for multiple ethane cycles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific examples and experimental data. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The specific embodiment is as follows: a large-scale synthesis method of low-cost Cu (BDC), which comprises the following steps: mixing copper nitrate trihydrate, terephthalic acid and DMF, and stirring until the mixture is clear to obtain a mixed solution; transferring the obtained hydrothermal precursor into a glass bottle, and placing the glass bottle into a constant-temperature drying oven to perform hydrothermal reaction at the temperature of 110-130 ℃; and filtering, washing and drying a sample obtained by the reaction to obtain the Cu (BDC) material.
A production process for separating low-concentration ethane in ethane-ethylene mixed gas, which comprises the following steps: introducing ethane-ethylene mixed gas into an adsorption column filled with the Cu (BDC) adsorbent prepared by the low-cost Cu (BDC) large-scale synthesis method, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out dynamic adsorption penetration experiments under certain temperature and pressure; monitoring the concentration of ethane and ethylene at the outlet of the adsorption column in real time by adopting gas chromatography; the desorption regeneration of the adsorbent is completed by inert gas purging at room temperature or under the condition of vacuumizing negative pressure.
In the synthesis process, the method controls the same reaction space, adjusts the dosage of the solvent, and synthesizes more products in a smaller space as much as possible, thereby saving the reaction space, reducing the synthesis cost, and having the advantages of low-cost and easily-obtained raw materials, simple synthesis and high yield. The high-efficiency separation method for separating low-concentration ethane in the ethane-ethylene mixed gas is simple in steps, can generate polymer grade ethylene product gas (> 99.99%) through one-step adsorption separation, and is expected to realize industrial application of Cu (BDC) materials.
In some embodiments, the addition amount of copper nitrate trihydrate and terephthalic acid are in equimolar amounts, the amount of DMF solvent is controlled to be 150-250 mL, the reaction temperature is controlled to be 110-130 ℃, and the reaction time is 24-48 h.
The invention is not limited to such yields at this ratio, and yields obtained at other scaling up or down ratios are equally applicable to the invention.
The metal salts and ligands used in the synthesis process in some embodiments are inexpensive and are one of the least costly materials of all ethane-selective MOFs materials reported to date.
In some embodiments, the volume fraction of ethane in the mixed gas is 0-50% and does not contain zero.
In some embodiments, the sample filled in the adsorption column is 1-2 g, the flow rate of the ethane-ethylene mixed gas entering the adsorption column is 0-5 mL/min, and when ethane is adsorbed on the adsorbent, the adsorption temperature is 0-25 ℃ and the pressure is 1 bar or more.
In some specific embodiments, cu (BDC) can realize the high-efficiency separation of ethane and ethylene, and the polymerization grade ethylene product gas can be generated through one-step adsorption separation>99.99 percent) and the yield of the high-purity ethylene obtained by one-time penetration experiment is 15-20 cm 3 /g。
Specific examples are exemplified below.
Example 1
Weighing 19.36 g copper nitrate trihydrate and 13.28 g terephthalic acid, weighing 200 mL DMF, mixing, and stirring until the mixture is clear to obtain a mixed solution; transferring the obtained hydrothermal precursor into a 250 mL glass bottle, and placing the glass bottle into a constant-temperature drying oven to perform hydrothermal reaction at the temperature of 110-130 ℃; and filtering, washing and drying a sample obtained by the reaction to obtain the Cu (BDC) material. The yield was 24.12. 24.12 g, 80.40%.
Example 2
The activation condition of the test sample is 200-250 ℃, the sample is subjected to degassing activation for 2-4 hours under vacuum, then the gas adsorption separation performance test of the sample is carried out, and the pressure range of the test sample is 0-1 bar.
Example 3
To evaluate the actual separation effect of Cu (BDC) on the ethane and ethylene mixtures, dynamic breakthrough experiments of the ethane/ethylene mixtures were performed using the apparatus shown in fig. 7. About 1-2 g of the sample is loaded into a stainless steel adsorption column with an inner diameter of 4 mm and a length of 125 mm; purging residual gas in the pipeline by high-purity inert purge; the sample adsorption column is fixed in the indoor device, and the flow rates of ethane and ethylene are regulated by a pressure valve and a flowmeter at the inlet of the adsorption column; monitoring the concentration of ethane and ethylene at the outlet of the adsorption column in real time by gas chromatography (490 Micro GC, agilent Technologies); the whole experiment is carried out at 0-25 ℃, and the flow rate of the ethane/ethylene mixture (1:1 and 1:9, v/v) is 0-5 mL/min.
In the synthesis process of Cu (BDC), copper nitrate trihydrate and terephthalic acid as ligand are adopted as metal salts, and the two reaction raw materials are low in price and easy to obtain, so that the raw material cost is greatly saved. The whole synthesis process is relatively convenient, and the product can be directly obtained by only putting a glass bottle containing the hydrothermal precursor into a baking oven with the temperature of 100-120 ℃ for reaction for 24-48 hours. At the laboratory synthesis level, the cost of synthesizing 1 gram of Cu (BDC) is only 1.21 yuan per gram. Structurally, it has a one-dimensional pore structure (5.7x5.1 a 2 ). Copper metal binds to oxygen in ligand BDC, maintaining the pad-writeAnd the structure, the pore canal structure and the size of the structure are beneficial to the adsorption separation of ethane and ethylene.
In addition, the XRD contrast pattern of the experimentally obtained Cu (BDC) and the simulated peaks verifies the material composition. As can be seen from fig. 3, the XRD diffraction peaks of Cu (BDC) prepared by the method of the present invention are consistent with the simulated peaks of the original structure, indicating that the method successfully synthesizes Cu (BDC) material.
FIG. 4 is an SEM image of Cu (BDC), and the synthesized sample is a cubic structure with cracks on the surface and a size of about 5. Mu.m. FIG. 5 shows the adsorption and desorption curve of Cu (BDC) at 77K for nitrogen, the curve being a typical type I isotherm, conforming to the characteristics of microporous materials, measured S BET =581 m 2 /g。
The adsorption and desorption effects of Cu (BDC) on ethane and ethylene can be seen from fig. 6. The adsorption and desorption curve at 298K, cu (BDC), which showed greater adsorption of ethane than ethylene throughout the entire test range, showed Cu (BDC) to be an ethane selective adsorbent.
As shown in FIG. 8, it is known from the penetration experiment of Cu (BDC) on the mixture of ethane and ethylene with different proportions at room temperature that when the mixture is C 2 H 6 /C 2 H 4 (volume fraction ratio of 1/1 and 1/9), the material can be obtained from C 2 H 6 /C 2 H 4 Effective separation of ethane impurities from the mixture to achieve C 2 H 6 /C 2 H 4 Is effective in separation.
Cu (BDC) was subjected to various conditions and it can be seen from fig. 9a that the material remained its original structure after adsorption, penetration, high temperature activation and 6 months exposure to air. As can be seen from fig. 9b, 9c, after acid-base treatment, the Cu (BDC) structure is restored after activation, although structural transformation occurs. Further, the multiple ethane cycle adsorption isotherms of Cu (BDC) of fig. 10 indicate that Cu (BDC) performance is unchanged after multiple adsorption and desorption.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (4)

1. The application of Cu (BDC) in separating low-concentration ethane in an ethane-ethylene gas system is characterized in that the synthesis method of the Cu (BDC) comprises the steps of mixing a copper source, terephthalic acid and DMF, and stirring until the mixture is clear to obtain a mixed solution; transferring the obtained hydrothermal precursor into a container, and placing the container into a constant-temperature drying oven for hydrothermal reaction; filtering, washing and drying a sample obtained by the reaction to obtain a Cu (BDC) material; the molar amounts of the copper source and the terephthalic acid are equal; the temperature of the hydrothermal reaction is 110-130 ℃, and the reaction time is 24-48 h; the copper source is copper acetate or copper nitrate; wherein, in the ethane ethylene gas system, the volume fraction of ethane is in the range of 0-50%, and the volume fraction of ethane is not zero.
2. Use of Cu (BDC) according to claim 1 for the separation of low concentration ethane in an ethane ethylene gas system, characterized in that the specific steps of Cu (BDC) for the separation of low concentration ethane in an ethane ethylene gas system are: introducing ethane-ethylene mixed gas into an adsorption column filled with Cu (BDC) material, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out dynamic adsorption penetration experiment under certain temperature and pressure; the concentrations of ethane and ethylene were monitored in real time by gas chromatography at the outlet of the adsorption column.
3. Use of Cu (BDC) according to claim 2 for separating low concentration ethane in ethane-ethylene gas systems, characterized in that the Cu (BDC) packing in the adsorption column is 1-2 g, the flow of ethane-ethylene mixture into the adsorption column is 0-5 mL/min, the adsorption temperature is 0-25 ℃ and the pressure is 1 bar or more when ethane is adsorbed on the adsorbent.
4. Use of Cu (BDC) according to claim 1 for separating low concentration ethane in ethane-ethylene gas systems, characterized in thatCu (BDC) can realize the high-efficiency separation of ethane and ethylene, and can generate polymer grade ethylene product gas through one-step adsorption separation, and the yield of high-purity ethylene obtained through one-step penetration experiment is 15-20 cm 3 /g。
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