CN114261970B - Transition metal oxide molecular sieve and preparation method and application thereof - Google Patents
Transition metal oxide molecular sieve and preparation method and application thereof Download PDFInfo
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- CN114261970B CN114261970B CN202111354560.3A CN202111354560A CN114261970B CN 114261970 B CN114261970 B CN 114261970B CN 202111354560 A CN202111354560 A CN 202111354560A CN 114261970 B CN114261970 B CN 114261970B
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Abstract
The transition metal oxide molecular sieve disclosed by the invention is named MoPO, and the molecular formula is NH 4 P 6 Mo 13 O 48 The crystal system is cubic, the space group is IA-3, and the unit cell parameters are as follows:α＝90°，the transition metal oxide molecular sieve is a three-dimensional framework porous material with a building unit based on a cubic structure, wherein [ Mo ] 13 O 48 ]The number of building units in a cell is 8, and the number of connection points is 8. The molecular sieve has the characteristics of high stability, high mass transfer rate, high porosity, reusability, ion exchange and the like, can be used as an adsorbent for the adsorption separation of low-carbon hydrocarbon, has obviously different adsorption properties particularly to ethylene and acetylene, can effectively separate the mixed gas of ethylene and acetylene to obtain high-purity ethylene or acetylene, saves energy, is environment-friendly, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of inorganic material and porous material preparation, in particular to a transition metal oxide molecular sieve based on Mo and P, and a preparation method and application thereof.
Background
The separation of gases is a major difficulty in industry, and traditional industrial separations rely on cryogenic distillation techniques. The physical properties of different gases, such as boiling point, size and polarity, are different, the distillation technology mainly depends on the difference of the boiling points of the gases, and the method has the advantages of high energy consumption, high cost and environmental protection. Adsorption separation is oneThe novel separation technology relies on porous materials to realize molecular sieving on gases with different sizes and polarities, and has the advantages of high efficiency, low cost and environmental protection, but due to the gases with the same carbon number, such as C 2 The kinetic diameters between hydrocarbons are similar, and separation remains a major difficulty.
Ethylene is an industrially important raw material, and is a raw material for synthetic fibers, synthetic rubber, synthetic plastics, etc., and is also used as a ripening agent for fruits and vegetables. The ethylene industry is the heart of the petrochemical industry, and the C produced in the petrochemical industry 2 The separation of ethylene from the mixed gas is of great importance, wherein the separation of ethylene and acetylene is a step with great separation difficulty, and the separation is realized mainly by the principle of difference of boiling points between gases at present, but the energy consumption is huge, and a new separation technology needs to be developed.
The focus of research today is the development of new adsorbents to achieve more efficient, lower cost, more stable separations. At present, the metal organic frame is adsorption separation C 2 The main stream material of hydrocarbon, however, the synthetic cost of the metal organic frame is high, and the industrialization is not easy. Porous inorganic metal oxides have high stability and low cost characteristics compared to metal organic frameworks, and can adsorb lower hydrocarbons such as C 2 The hydrocarbons are expected to have a certain application prospect in the separation of low-carbon hydrocarbons, especially ethylene and acetylene.
The properties of the nano particles in the material have larger influence on the adsorption performance, for example, the larger crystals in the metal organic frame can cause the mass transfer rate to be reduced, and the smaller nano particles can be beneficial to the increase of the mass transfer rate, so that the adsorption performance of the material is improved, and further the gas separation performance is improved.
In order to solve the problems that the cost of a metal organic framework adsorbent is too high, and mass transfer rate is reduced due to large crystals to influence separation performance, molybdenum-phosphorus oxide nano particles with ordered micropores with higher porosity are developed, higher adsorption capacity of low-carbon hydrocarbon is realized, the preparation method is simpler, the cost is lower, and the transition metal oxide molecular sieve based on Mo and P and the preparation method and application thereof are provided accordingly.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the transition metal oxide molecular sieve which has high stability, high mass transfer rate, high porosity, reusability and ion exchange, the preparation method and the application thereof, and the molecular sieve can be used as an adsorbent for the adsorption separation of low-carbon hydrocarbon, particularly for the obvious difference of the adsorption performance of ethylene and acetylene, can effectively separate the mixed gas of ethylene and acetylene, and can obtain high-purity ethylene or acetylene, thereby saving energy and protecting the environment and having good application prospect.
The technical scheme adopted for solving the technical problems is as follows: a transition metal oxide molecular sieve is named MoPO and has a molecular formula of NH 4 P 6 Mo 13 O 48 The crystal system is cubic, the space group is IA-3, and the unit cell parameters are as follows:α＝90°，/>the transition metal oxide molecular sieve is a three-dimensional framework porous material with a building unit based on a cubic structure, wherein [ Mo ] 13 O 48 ]The number of building units in a cell is 8, and the number of connection points is 8.
The preparation method of the transition metal oxide molecular sieve comprises the following steps:
(1) Adding 0.6-0.8 g of molybdate and 0.2-0.4 g of reducing agent into 7-20 mL of water, and stirring for 5-10 minutes to obtain a mixed solution;
(2) Adding 1.0-2.0 g of diammonium hydrogen phosphate into the mixed solution obtained in the step (1), then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 5-7, and stirring for 12-48 hours to obtain the mixed solution;
(3) Adding the mixed solution obtained in the step (2) into a 25mL reaction kettle liner, and performing hydrothermal reaction for 12-24 hours at 150-250 ℃ to obtain a reaction solution;
(4) And (3) centrifuging, washing and drying the reaction liquid obtained in the step (3), wherein the obtained solid product is the transition metal oxide molecular sieve.
Preferably, the molybdate adopted in the step (1) is ammonium molybdate tetrahydrate or sodium molybdate dihydrate, and the reducing agent adopted is hydrazine sulfate or metallic molybdenum powder.
Preferably, the concentration of the dilute sulfuric acid used in step (2) is 0.5 to 2.0M.
Preferably, the drying temperature used in step (4) is 60 to 80 ℃.
The application of the transition metal oxide molecular sieve in the mixed gas for selectively separating ethylene and acetylene.
Compared with the prior art, the invention has the following advantages:
1) The transition metal oxide molecular sieve has high stability, small crystal with nanometer scale and high mass transfer rate, has the characteristics of high porosity, reusability, ion exchange and the like, can be used as an adsorbent for the adsorption separation of low-carbon hydrocarbon, particularly has obviously different adsorption properties on ethylene and acetylene, can effectively separate the mixed gas of ethylene and acetylene to obtain high-purity ethylene or acetylene, saves energy and is environment-friendly, and has good application prospect;
2) The preparation method adopts a hydrothermal synthesis method, and obtains the transition metal oxide molecular sieve with good crystallinity assembled by polyoxometallate octahedrons under high temperature and high pressure by regulating and controlling the amount of reducing agent, pH value, reaction time and other factors, the operation is simple, the cost of required raw materials is low, and the preparation method is a novel transition metal oxide molecular sieve which is different from the traditional metal organic framework and zeolite material.
Drawings
FIG. 1 is an SEM image of a transition metal oxide molecular sieve prepared in example 1;
FIG. 2 is a graph showing the particle size distribution of the transition metal oxide molecular sieve prepared in example 1;
FIG. 3 is a diagram of the construction unit in the transition metal oxide molecular sieve prepared in example 1 to example 3;
FIG. 4 is a diagram of 2X 2 unit cells;
FIG. 5 is an XRD pattern of the transition metal oxide molecular sieves prepared in examples 1 to 3;
FIG. 6 is a graph showing the nitrogen adsorption and desorption curves of the transition metal oxide molecular sieve prepared in example 1;
FIG. 7 is a pore size distribution diagram of the transition metal oxide molecular sieve prepared in example 1;
FIG. 8 is a graph showing the ethylene-acetylene single-component adsorption curve of the transition metal oxide molecular sieve prepared in example 2;
fig. 9 is a dynamic breakthrough separation curve of vinylacetylene for the transition metal oxide molecular sieve prepared in example 3.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1: 0.6128g of ammonium molybdate tetrahydrate and 0.3254g of hydrazine sulfate are added into 20mL of water and stirred for 5 minutes to obtain a mixed solution; then adding 1.1875g of diammonium hydrogen phosphate into the obtained mixed solution, then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 5, and stirring for 24 hours to obtain the mixed solution; adding the obtained mixed solution into a 25mL reaction kettle liner, and performing hydrothermal reaction for 16 hours at 230 ℃ to obtain a reaction solution; finally, the obtained reaction solution was centrifuged at 3500rpm for 5 minutes, washed and dried at 80℃for 6 hours to obtain a solid product, namely, the compound MoPO of example 1.
Example 2: 0.6128g of ammonium molybdate tetrahydrate and 0.24g of metallic molybdenum powder are added into 15mL of water and stirred for 5 minutes to obtain a mixed solution; then adding 1.1875g of diammonium hydrogen phosphate into the obtained mixed solution, then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 7, and stirring for 24 hours to obtain the mixed solution; adding the obtained mixed solution into a 25mL reaction kettle liner, and performing hydrothermal reaction for 16 hours at 175 ℃ to obtain a reaction solution; finally, the obtained reaction solution was centrifuged at 3500rpm for 5 minutes, washed and dried at 80℃for 6 hours to obtain a solid product, namely the compound MoPO of example 2.
Example 3: 0.6128g of ammonium molybdate tetrahydrate and 0.1627g of hydrazine sulfate are added into 20mL of water and stirred for 5 minutes to obtain a mixed solution; then adding 1.1875g of diammonium hydrogen phosphate into the obtained mixed solution, then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 6, and stirring for 24 hours to obtain the mixed solution; adding the obtained mixed solution into a 25mL reaction kettle liner, and performing hydrothermal reaction for 16 hours at 230 ℃ to obtain a reaction solution; finally, the obtained reaction solution was centrifuged at 3500rpm for 5 minutes, washed and dried at 80℃for 6 hours to obtain a solid product, namely the compound MoPO of example 3.
The SEM image of the transition metal oxide molecular sieve prepared in example 1 is shown in fig. 1, the particle size distribution diagram is shown in fig. 2, and it can be seen from fig. 2 that the prepared transition metal oxide molecular sieve has small crystals of nano scale. XRD patterns of the transition metal oxide molecular sieves prepared in examples 1 to 3 are shown in FIG. 5. The nitrogen adsorption and desorption curves and pore size distribution diagrams of the transition metal oxide molecular sieve prepared in example 1 are shown in fig. 6 and 7, respectively. The ethylene acetylene single component adsorption curve of the transition metal oxide molecular sieve prepared in example 2 is shown in fig. 8. The dynamic breakthrough separation curve of vinylacetylene of the transition metal oxide molecular sieve prepared in example 3 is shown in fig. 9.
Elemental analysis (for the transition metal oxide molecular sieve prepared in example 2) results, experimental values (%): mo,37.19; p,5.98. According to formula NMo 13 P 6 O 110 H 128 The theoretical values of (2) are: mo,37.41; p,5.58.
FT-IR(KBr,cm -1 ):1636,1400,1101,1045,991,945,912,743,721,613,555,519,492。
The structure of the transition metal oxide molecular sieve prepared in example 2 was determined as follows: selecting material powder, grinding the material powder properly, tabletting, taking a Bruker D8 powder diffractometer Cu-K alpha as a diffraction light source, and collecting diffraction signals at room temperature within the range of 2 theta of 5 degrees or more and 90 degrees or less. Mo was solved by direct method using Fullprof software. The P and O atoms are predicted using VASP according to DFT theory calculations. The crystallographic data are shown in Table 1. The selected partial bond lengths and bond angles are shown in Table 2.
TABLE 1 Crystal data Table of Compound MoPO prepared in example 2
TABLE 2 partial bond lengths and bond angles of the MoPO compounds prepared in EXAMPLE 2
| Atoms | Key length | Atoms | Key length | Atoms | Key length |
| Mo2-O5 | 2.172 | Mo1-O5 | 2.044 | O7-Mo2 | 2.019 |
| Mo2-O6 | 2.000 | Mo1-O7 | 2.177 | O7-Mo1 | 2.177 |
| Mo2-O8 | 1.987 | O3-P1 | 1.770 | O8-Mo2 | 1.987 |
| Mo2-O7 | 2.019 | O3-Mo2 | 1.770 | O9-Mo2 | 2.065 |
| Mo2-O3 | 1.770 | O4-Mo1 | 1.744 | O9-Mo1 | 2.104 |
| Mo2-O9 | 2.065 | O4-P1 | 1.775 | O10-Mo1 | 1.984 |
| Mo1-O6 | 1.871 | O5-Mo3 | 2.307 | P1-O3 | 1.770 |
| Mo1-O4 | 1.744 | O5-Mo2 | 2.172 | Mo3-O5 | 2.307 |
| Mo1-O10 | 1.984 | O5-Mo1 | 2.044 | Mo3-O5 | 2.307 |
| Mo1-O9 | 2.104 | O6-Mo2 | 2.000 | Mo3-O5 | 2.307 |
| P1-O4 | 1.775 | O6-Mo1 | 1.871 | Mo2-O5 | 2.307 |
| Mo2-O5 | 2.307 |
FIG. 3 is an embodiment1 to 3. FIG. 4 is a diagram of 2X 2 unit cells. Single crystal structural analysis shows that the compound MoPO is cubic space group IA-3 and the compound MoPO is [ Mo ] 13 O 48 ]As the building blocks, the number of the building blocks in a unit cell was 8. Each building unit consists of 6 PO' s 4 The tetrahedron is assembled with 6 adjacent building units around. The molecular sieve material has three-dimensional pore canal, the crystallographic size of the pore canal is 0.38nm, and one part of the three-dimensional pore canal is NH 4 + Occupied, the other part is occupied by water molecules. After removing the water molecules in the pore canal, the material has the basic structural characteristics of selective adsorption separation and can be a potential separation material.
The compound MoPO of example 1 was subjected to a nitrogen adsorption and desorption test. And (3) carrying out activation at 100 ℃ for 2 hours under vacuum to remove water molecules in the pore channels of the material. The test temperature was-198 deg.c and the test results are shown in fig. 6 and 7. The results show that the curve is a type I adsorption curve, the product is a microporous material, and the BET specific surface area is 109m 2 Per g, pore volume of 0.0372cm 3 And/g, pore diameter of 0.38nm.
The compound MoPO of example 2 was tested for ethylene and acetylene adsorption properties. And (3) carrying out activation at 100 ℃ for 2 hours under vacuum to remove water molecules in the pore channels of the material. The test temperature was 0℃and the test results are shown in FIG. 8. The result shows that the material has higher adsorption capacity to acetylene, reaching 30cm 3 Per g, and an ethylene adsorption capacity of 15cm 3 /g, meaning that the material has a greater potential for acetylene and ethylene separation.
The compound MoPO of example 3 was tested for dynamic separation properties of ethylene and acetylene. 1g of the compound MoPO of example 3 was packed in an adsorption column, activated at 100℃for 2 hours under vacuum to remove water molecules in the pores of the material, followed by testing at 0.3mL/min and 0.3mL/min for ethylene and acetylene, 5mL/min for He as a purge gas, peak detection by chromatography for gas, and 0℃for test temperature. The result shows that the material has certain separation performance on ethylene and acetylene, ethylene breaks through first, and breaks through after about 20 minutes, and the adsorption quantity of acetylene is higher than that of ethylene after about 40 minutes, and the break-through time difference of the two gases is 20 minutes.
The basic structure of the material is determined by the characterization means such as infrared ray, X-ray diffraction and the like, so that the transition metal oxide molecular sieve with high porosity is obtained, is applied to the separation of ethylene and acetylene, provides reference significance for the synthesis of the transition metal oxide molecular sieve with a metal oxide octahedron as a basic structural unit, and provides reference in the aspect of diversification of gas separation materials.
Claims (6)
1. A transition metal oxide molecular sieve is characterized in that the transition metal oxide molecular sieve is named MoPO and has a molecular formula of NH 4 P 6 Mo 13 O 48 The crystal system is cubic, the space group is IA-3, and the unit cell parameters are as follows:α＝90°，the transition metal oxide molecular sieve is a three-dimensional framework porous material with a building unit based on a cubic structure, wherein [ Mo ] 13 O 48 ]The number of the construction units in the unit cell is 8, and the number of the connection points is 8; the preparation method of the transition metal oxide molecular sieve comprises the following steps:
(1) Adding 0.6-0.8 g of molybdate and 0.2-0.4 g of reducing agent into 7-20 mL of water, and stirring for 5-10 minutes to obtain a mixed solution;
(2) Adding 1.0-2.0 g of diammonium hydrogen phosphate into the mixed solution obtained in the step (1), then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 5-7, and stirring for 12-48 hours to obtain the mixed solution;
(3) Adding the mixed solution obtained in the step (2) into a 25mL reaction kettle liner, and performing hydrothermal reaction for 12-24 hours at 150-250 ℃ to obtain a reaction solution;
(4) And (3) centrifuging, washing and drying the reaction liquid obtained in the step (3), wherein the obtained solid product is the transition metal oxide molecular sieve.
2. The method for preparing the transition metal oxide molecular sieve according to claim 1, comprising the steps of:
(1) Adding 0.6-0.8 g of molybdate and 0.2-0.4 g of reducing agent into 7-20 mL of water, and stirring for 5-10 minutes to obtain a mixed solution;
(2) Adding 1.0-2.0 g of diammonium hydrogen phosphate into the mixed solution obtained in the step (1), then adding a certain amount of dilute sulfuric acid to regulate the pH value of the mixed solution to 5-7, and stirring for 12-48 hours to obtain the mixed solution;
(3) Adding the mixed solution obtained in the step (2) into a 25mL reaction kettle liner, and performing hydrothermal reaction for 12-24 hours at 150-250 ℃ to obtain a reaction solution;
(4) And (3) centrifuging, washing and drying the reaction liquid obtained in the step (3), wherein the obtained solid product is the transition metal oxide molecular sieve.
3. The method for preparing a transition metal oxide molecular sieve according to claim 2, wherein the molybdate used in the step (1) is ammonium molybdate tetrahydrate or sodium molybdate dihydrate, and the reducing agent used is hydrazine sulfate or metallic molybdenum powder.
4. The method for producing a transition metal oxide molecular sieve according to claim 2, wherein the concentration of the dilute sulfuric acid used in the step (2) is 0.5 to 2.0M.
5. The method for preparing a transition metal oxide molecular sieve according to claim 2, wherein the drying temperature used in the step (4) is 60 to 80 ℃.
6. Use of the transition metal oxide molecular sieve of claim 1 for selectively separating a mixture of ethylene and acetylene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB777232A (en) * | 1953-12-24 | 1957-06-19 | Union Carbide & Carbon Corp | Crystalline synthetic zeolites |
| CN108014751A (en) * | 2016-11-03 | 2018-05-11 | 浙江大学 | A kind of method that ethene and acetylene are separated from gaseous mixture |
| JP2021127272A (en) * | 2020-02-14 | 2021-09-02 | 学校法人神奈川大学 | Composite oxide and its production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB777232A (en) * | 1953-12-24 | 1957-06-19 | Union Carbide & Carbon Corp | Crystalline synthetic zeolites |
| CN108014751A (en) * | 2016-11-03 | 2018-05-11 | 浙江大学 | A kind of method that ethene and acetylene are separated from gaseous mixture |
| JP2021127272A (en) * | 2020-02-14 | 2021-09-02 | 学校法人神奈川大学 | Composite oxide and its production method |
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