CN112657471B - Preparation method of low-concentration acetylene efficient trapping agent - Google Patents
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Abstract
The invention relates to a preparation method of a low-concentration acetylene high-efficiency trapping agent, wherein the trapping agent is Zn2(bpy) (btec) metal organic framework material, the specific preparation method is as follows: adding a zinc source, pyromellitic dianhydride and 4,4' -bipyridyl into deionized water, stirring and mixing uniformly, adding ammonia water or ammonium salt, stirring for a period of time, filtering and washing the obtained precipitate, and drying the filter cake to obtain the trapping agent. Preparation of Zn by the Process of the invention2When the (bpy) (btec) organic framework material is used, high temperature and high pressure are not needed like hydrothermal synthesis, the preparation method is simpler, the product yield is high, and the method is suitable for industrial production2(bpy) (btec) has smaller granularity and a loose structure compared with the traditional hydrothermal method, and shows more excellent trapping effect on the high-efficiency trapping of low-concentration acetylene.
Description
Technical Field
The invention relates to a gas separation technology, in particular to a preparation method of a low-concentration acetylene high-efficiency trapping agent.
Background
Acetylene is an important petrochemical basic raw material, about 1% of acetylene impurities exist in the traditional process of preparing ethylene by naphtha cracking, and in order to obtain polymerization-grade ethylene, the acetylene is converted into the ethylene by a noble metal catalytic reaction hydrogenation mode. However, in order to ensure that the concentration of acetylene in ethylene is reduced to below 10ppm, the selectivity is obviously reduced while high conversion rate is maintained, and a part of ethylene products are excessively hydrogenated to generate ethane, so that not only is the waste of ethylene products caused, but also the task of later ethane/ethylene separation is aggravated. If the method can realize the high-efficiency separation and enrichment of the low-concentration acetylene component in the ethylene or the related low-carbon hydrocarbon component to obtain the high-purity chemical product grade acetylene, the method has great significance. As can be seen from the ethylene production process, the main gas components in the application scenario involving acetylene separation are acetylene, ethylene, ethane and carbon dioxide. For the adsorption separation process, the main adsorption separation mechanisms are mainly divided into three types, namely thermodynamic separation, kinetic separation and size screening, in order to realize high-selectivity acetylene capture and desorption to obtain a high-purity acetylene product, and meanwhile, the process cannot cause overhigh adsorption heat, so the size screening mechanism is more suitable.
The Metal Organic Framework (MOF) material has a highly ordered three-dimensional pore channel structure, finely adjustable pore channel sizes and rich functional pore channel surfaces, shows great application potential in the field of gas adsorption and separation in recent years, can develop an MOF material capable of industrially preparing, separating and adsorbing low-concentration acetylene and has great application prospects. However, in the prior art, the severe preparation conditions and low yield of MOF restrict the large-scale application of MOF in the field of gas separation.
Disclosure of Invention
The invention provides a low-concentration acetylene high-efficiency trapping agent Zn2(bpy) (btec) preparation method, Zn reduction2(bpy) (btec) preparation difficulty, yield improvement and obtained product quality improvement, Zn prepared by the method2(bpy) (btec) can be used for efficient selective separation and adsorption of low-concentration acetylene.
The technical scheme adopted by the invention is as follows:
a preparation method of a low-concentration acetylene high-efficiency trapping agent comprises the following steps:
step 1: adding a zinc source, pyromellitic dianhydride and 4,4' -bipyridyl into deionized water, and stirring;
step 2: stirring and mixing evenly, then adding ammonia water or ammonium salt, and continuously stirring and reacting for a period of time;
and step 3: after the reaction is finished, filtering, washing and drying the obtained precipitate to obtain the chemical formula [ Zn ]2(bpy)(btec)(H2O)2]·2H2A collector of a metal-organic framework of O.
Further, in step 1, the total molar concentrations of the zinc source, pyromellitic dianhydride and 4,4' -bipyridine are: 1.2-1.8 mol/L.
Further, in step 1, the molar amount of pyromellitic dianhydride and the molar amount of 4,4' -bipyridine were equal.
Further, the molar amount of the zinc source: the molar weight of 4,4' -bipyridine = 1.3-3.3.
Further, in step 2, the molar amount of ammonia or ammonium salt: the molar weight of the pyromellitic dianhydride = 0.03-0.15.
Further, in the step 2, the reaction temperature is controlled to be 20-50 ℃, and the reaction time is controlled to be 0.5-2 h.
Further, the zinc source is zinc acetate or zinc nitrate.
Further, in step 3, a volume ratio of 1:1 as a precipitation washing solution.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1) compared with the traditional preparation method, the method adopts the method of adding ammonia water or ammonium salt and stirring and synthesizing at lower temperature, the whole step is quicker, simpler and more convenient, the ammonia water or ammonium salt can form pyromellitic acid ammonium salt, the solubility of pyromellitic dianhydride is obviously improved, the combination of pyromellitic dianhydride and Zn ions in aqueous solution is accelerated, the quick growth of MOF is promoted, and the yield is finally improved, thereby solving the problems that the prior art needs high temperature and long reaction time during hydrothermal synthesis and [ Zn ] is synthesized at lower temperature2(bpy)(btec)(H2O)2]·2H2The yield of O is low, thus being beneficial to industrial scale preparation;
2) compared with the MOF prepared by the traditional hydrothermal method, the MOF prepared by the invention has smaller granularity, a loose structure and more excellent trapping effect on the efficient trapping of low-concentration acetylene.
Drawings
FIG. 1 is an SEM photograph of the collectors obtained in example 1 and comparative examples 1 and 2.
FIG. 2 shows the collectors obtained in example 1 and comparative example 1, [ Zn ]2(bpy)(btec)(H2O)2]·2H2XRD pattern of O theoretical structure crystal form.
FIG. 3 shows a pair of trapping agents C obtained in example 12H2、C2H4And CO2Adsorption curve of (2).
FIG. 4 is a graph showing the adsorption curves of the collector obtained in example 1 for lower hydrocarbons.
FIG. 5 shows the trapping agent vs. CO obtained in example 12、H2、O2And N2Adsorption curve of (2).
FIG. 6 shows that when the mixed gas is C2H2/C2H4(1/99), the breakthrough curve and desorption curve of the trapping agent obtained in example 1.
FIG. 7 shows that when the mixed gas is C2H2/CO2(50/50), the breakthrough curve and desorption curve of the trapping agent obtained in example 1.
FIG. 8 shows that when the mixed gas is CH4/C2H2/C2H4/C2H6/C3H6/C3H8/CO2/H2(30/1/10/25/10/10/1/13), the breakthrough curve and desorption curve of the trapping agent obtained in example 1.
FIG. 9 shows that when the mixed gas is C2H2/C2H4(1/99), breakthrough cycling profile of the collector obtained in example 1.
FIG. 10 shows that when the mixed gas is C2H2/CO2(50/50), breakthrough cycling profile of the collector obtained in example 1.
FIG. 11 is a graph of example 1 and the prior art MOF vs. C2H2/C2H4(1/99) graph comparing performance at different pressures.
FIG. 12 is a graph of example 1 and the prior art MOF vs. C2H2/CO2(50/50) graph comparing performance at different pressures.
FIG. 13 shows the results of example 1 and the prior art MOF report for C2H2/C2H4(1/99) and C2H2/CO2(50/50) comparison of adsorption performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is described in detail below with reference to specific examples and experimental data, and it should be understood that the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.
The invention discloses a low-concentration C2H2A preparation method of a high-efficiency trapping agent, in particular to a metal organic framework material Zn2(bpy) (btec) preparation method, the material can be used for low concentration C2H2The efficient selective separation and adsorption method comprises the following specific preparation steps:
step 1: adding a zinc source, pyromellitic dianhydride and 4,4' -bipyridyl into deionized water, and stirring;
step 2: stirring and mixing evenly, then adding ammonia water or ammonium salt, and continuously stirring and reacting for a period of time;
and step 3: after the reaction is finished, filtering, washing and drying the obtained precipitate to obtain the chemical formula [ Zn ]2(bpy)(btec)(H2O)2]·2H2A collector of a metal-organic framework of O.
In the synthesis process, ammonia water or ammonium salt is added, which can form pyromellitic acid ammonium salt with pyromellitic dianhydride, and the combination of pyromellitic acid ammonium salt and Zn ions in the aqueous solution is accelerated to promote [ Zn ]2(bpy)(btec)(H2O)2]·2H2O grows rapidly and can increase [ Zn ]2(bpy)(btec)(H2O)2]·2H2The yield of O, thereby reducing the reaction temperature, the time required by the reaction and improving the product yield, and being beneficial to the industrialized preparation of the catalyst. The zinc source in this embodiment can be selected from zinc acetate, zinc sulfate, zinc nitrate, zinc chloride and other zinc sources, preferably zinc acetate or zinc nitrate, and other impurity elements such as S atoms or Cl atoms do not interfere with the synthesis of MOF, thereby possibly reducing the yield or quality of MOF.
In some embodiments, in step 1, the total molar concentration of the zinc source, pyromellitic dianhydride, and 4,4' -bipyridine is: 1.2 to 1.8mol/L to facilitate the formation of [ Zn ]2(bpy)(btec)(H2O)2]·2H2O。
In some embodiments, in step 1, the molar amount of pyromellitic dianhydride and the molar amount of 4,4' -bipyridine are equal to favor the formation of [ Zn ]2(bpy)(btec)(H2O)2]·2H2O, increasing the yield of MOF.
In some embodiments, in step 1, the molar amount of zinc source: the molar weight of 4,4' -bipyridyl = 1.3-3.3, and [ Zn ] is favorably formed2(bpy)(btec)(H2O)2]·2H2O, increasing the yield of MOF.
In some embodiments, in step 2, the molar amount of ammonia or ammonium salt: the molar weight of the pyromellitic dianhydride = 0.03-0.15, and the appropriate amount of ammonia water or ammonium salt is selected so as to form pyromellitic ammonium salt, which is beneficial to the formation of pyromellitic ammonium salt and Zn2+Bind to thereby promote [ Zn ]2(bpy)(btec)(H2O)2]·2H2O grows rapidly, and the invention finds that when the amount of ammonia water or ammonium salt is too high, the solution is alkaline, which can cause the reduction of the yield of the MOF.
In some specific embodiments, in the step 2, the reaction temperature is controlled to be 20-50 ℃, and the reaction time is controlled to be 0.5-2 h.
In some embodiments, in step 3, it is preferable to use a volume ratio of 1: the water/ethanol mixed solution of 1 is used as a precipitation washing liquid, the sources of the two washing liquids are easy to obtain, and under the mixing proportion, impurities and residual reactants on the MOF surface can be effectively and quickly washed, so that the purity of the product is improved. The invention is not limited to such washing solutions at this ratio, and other organic, inorganic or mixed solutions capable of effectively washing MOF precipitates are equally suitable for use in the invention.
Specific examples are exemplified below.
Example 1
Adding 0.150 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridine into 1.0L of deionized water, stirring and mixing uniformly, adding 2mL of ammonia water or ammonium salt with the mass concentration of 25%, controlling the temperature at 25 ℃, continuously stirring for 2 h, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
Example 2
Adding 0.150 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridine into 1.0L of deionized water, stirring and mixing uniformly, adding 2mL of ammonia water or ammonium salt with the mass concentration of 25%, controlling the temperature at 50 ℃, continuously stirring for 0.5 h, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
Example 3
Adding 0.150 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridine into 1.0L of deionized water, stirring and mixing uniformly, adding 3 mL of ammonia water or ammonium salt with the mass concentration of 25%, controlling the temperature at 50 ℃, continuously stirring for 0.5 h, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
Example 4
Adding 0.165 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridine into 1.0L of deionized water, stirring and mixing uniformly, adding 2mL of ammonia water or ammonium salt with the mass concentration of 25%, controlling the temperature at 30 ℃, continuously stirring for 0.5 h, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
Example 5
Adding 0.128 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridine into 1.0L of deionized water, stirring and mixing uniformly, adding 1mL of ammonia water or ammonium salt with the mass concentration of 25%, controlling the temperature at 20 ℃, continuously stirring for 0.5 h, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
Comparative example 1
0.1097 g of zinc acetate, 0.1091 g of pyromellitic dianhydride, 0.0781 g of 4,4' -bipyridine and 10 mL of deionized water are added into a 25mL reaction kettle, heated to 180 ℃ for five days, cooled to room temperature, filtered, washed by a hot water/ethanol (1: 1) mixed solution, and the obtained filter cake is dried to obtain the product.
Comparative example 2
Adding 0.128 kg of zinc acetate, 0.0764 kg of pyromellitic dianhydride and 0.0547 kg of 4,4' -bipyridyl into 1.0L of deionized water, controlling the temperature to be 20-50 ℃, stirring uniformly, mixing for 2 hours, filtering, washing with a water/ethanol (1: 1) mixed solution, and drying the obtained filter cake to obtain the product.
The yields of the products in the examples and comparative examples were calculated based on 4,4' -bipyridine, and the results are shown in Table 1.
TABLE 1 yield results for the products of the examples and comparative examples
As can be seen from Table 1, when hydrothermal synthesis is not adopted, the reaction temperature is directly reduced and the reaction time is shortened, the yield of the product is only 24.3%, while the method for preparing the product of the invention can improve the yield of the product and control the yield to 87.5%, the method is favorable for industrial preparation due to the adoption of low temperature and low pressure, and when hydrothermal synthesis is adopted, the yield of the product is 45.7%, but the product needs high temperature of 180 ℃ and needs 5 days of synthesis, which is not favorable for industrial production, and even if the product is industrially generated, the high temperature and high pressure state is not as efficient and safe as the method for preparing the product in a low temperature and short time.
To characterize Zn2The microscopic morphology of the (bpy) (btec) material is characterized by SEM of products obtained in example 1, comparative example 1 and comparative example 2, and the result is shown in FIG. 1, wherein b in FIG. 1 is an SEM image of example 1, a in FIG. 1 is an SEM image of comparative example 1, and c in FIG. 1 is an SEM image of comparative example 2, and as can be seen from the images, the sample of example 1 has smaller granularity and a loose structure, and is more beneficial to mass transfer and diffusion of gas compared with comparative example 1; comparative example 2 presents nano-scale agglomerates, reaction time and reaction temperature are low without addition of ammonia or ammonium salt, solubility of pyromellitic dianhydride in water is poor, resulting in [ Zn ]2(bpy)(btec)(H2O)2]·2H2The growth process of O is slow, and the granularity of the product is very low.
In order to confirm the crystal structure of the synthesized product, XRD characterization was performed on example 1 and comparative example 1, and the results were compared with [ Zn ]2(bpy)(btec)(H2O)2]·2H2The comparison results are shown in figure 2, and it can be seen from the figure that Zn with the theoretical crystal structure is obtained by adopting the invention and hydrothermal synthesis2(bpy) (btec) material.
To characterize Zn2(bpy) (btec) adsorption capacity of the material for different gases the adsorption curve of the product of example 1 for each gas was determined at 298K using a Micromeritics ASAP 2020 instrument, using the product of example 1, and FIG. 3 is C2H2, C2H4And CO2FIG. 4 is an adsorption curve of a lower hydrocarbon, and FIG. 5 is a adsorption curve of CO2, H2, O2And N2The adsorption curve of (a) is shown,
it can be seen from FIGS. 3-5 that Zn is present in a gas in which acetylene is mixed with an organic gas, mixed with an inorganic gas, or co-mixed with an organic or inorganic gas2The (bpy) (btec) material has excellent adsorption performance on acetylene and weak adsorption on other gases.
To test Zn2Actual separation effect of (bpy) (btec) material on different mixed gases, taking the product obtained in example 1 as an example, the penetration experiment and desorption experiment are carried out on the product obtained in example 1, and the specific process is as follows: accurately controlling the mixed gas to pass through an adsorption column (with the size of phi 4 multiplied by 275 mm) filled with an adsorbent (the sample amount is 3.0575 g) at the pressure (1.01 bar) and the flow rate (1.25 ml/min) through a pressure reducing valve and a gas mass flowmeter, controlling the temperature of the adsorbent to be 298K, starting timing at the same time, monitoring the concentration of tail gas in real time through a chromatograph (GC-2014C, TCD detector) at the tail end of the adsorption column, and recording data; and after the adsorption is saturated, switching to vacuum, starting timing, monitoring the tail gas concentration in real time through a chromatograph (GC-2014C, TCD detector) at the tail end of the adsorption column, recording data until the tail end cannot monitor the components of the feed gas, and considering that the desorption of the adsorption column is finished.
When the mixed gas is C2H2/C2H4(volume fraction ratio 1/99), the breakthrough and desorption curves of the adsorbent are shown in the left and right panels, respectively, of FIG. 6, from which it can be seen that the material is effective in separating C2H2/C2H4(1/99) the mixture was separated to obtain 98.5% pure acetylene.
When the mixed gas is C2H2/CO2(volume fraction ratio 50/50), the breakthrough and desorption curves of the adsorbent are shown in the left and right panels, respectively, of FIG. 7, from which it can be seen that the material is effective in separating C2H2/CO2(50/50) the mixture was separated to yield 92.5% pure acetylene.
When the mixed gas is CH4/C2H2/C2H4/C2H6/C3H6/C3H8/CO2/H2(30/1/10/25/10/10/1/13 volume fraction); the curves of the adsorbent and the desorption curve are respectively shown in the left graph and the right graph of fig. 8, and as can be seen from the graphs, the material can be used for efficiently separating the mixture and separating acetylene with the purity of more than 98.0 percent.
To test Zn2(bpy) (btec) stability of the material, exemplified by the product of example 1, the material was tested for penetration cycling curves when the gas mixture was C2H2/C2H4(1/99), the breakthrough cycle curves are shown in FIG. 9, where C2H4Is represented by a square, C2H2Represented by circles; when the mixed gas is C2H2/CO2(50/50), the breakthrough cycle curves are shown in FIG. 10, where CO2Represented by triangles, C2H2Indicated by circles, it can be seen from FIGS. 9 and 10 that Zn is present after 5 consecutive cycles2The performance of the (bpy) (btec) material is fully maintained.
FIGS. 11-13 show the mixed gas C of example 1 and the MOF reported in the prior art under the condition of 1bar and 298K2H2/C2H4(1/99) and C2H2/CO2(50/50)The graph shows that the adsorbent shows excellent adsorption selectivity, which is far superior to the reported MOF material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of a low-concentration acetylene high-efficiency trapping agent is characterized by comprising the following steps:
step 1: adding a zinc source, pyromellitic dianhydride and 4,4' -bipyridyl into deionized water, and stirring;
step 2: stirring and mixing evenly, then adding ammonia water or ammonium salt, and continuously stirring and reacting for a period of time;
and step 3: after the reaction is finished, filtering, washing and drying the obtained precipitate to obtain the chemical formula [ Zn ]2(bpy)(btec)(H2O)2]·2H2A collector of a metal-organic framework of O.
2. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to claim 1, wherein in the step 1, the total molar concentration of the zinc source, the pyromellitic dianhydride and the 4,4' -bipyridine is as follows: 1.2-1.8 mol/L.
3. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to claim 1, wherein in the step 1, the molar amount of pyromellitic dianhydride and the molar amount of 4,4' -bipyridine are equal.
4. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to any one of claims 1 to 3, wherein in the step 1, the molar weight of the zinc source is as follows: the molar weight of 4,4' -bipyridine = 1.3-3.3.
5. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to claim 1, wherein in the step 2, the molar amount of ammonia water or ammonium salt is as follows: the molar weight of the pyromellitic dianhydride = 0.03-0.15.
6. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to claim 1, wherein in the step 2, the reaction temperature is controlled to be 20-50 ℃, and the reaction time is controlled to be 0.5-2 h.
7. The method for preparing the low-concentration acetylene high-efficiency capturing agent according to claim 1, characterized in that the zinc source is zinc acetate or zinc nitrate.
8. The method for preparing the low-concentration acetylene high-efficiency trapping agent according to claim 1, characterized in that in the step 3, the volume ratio of 1:1 as a precipitation washing solution.
9. The method of claim 1, wherein the ammonium salt is ammonium nitrate or ammonium bicarbonate.
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