Application of MOF separation material in N2/O2 separation

A separation material and molecular formula technology, applied in the application field of MOF separation material in N2/O2 separation, can solve the problem of large energy consumption

Pending Publication Date: 2022-01-11
郑州密斯卡化工科技有限公司
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The PSA process needs to have high N2 adsorption capacity and N 2 / O 2 Selective adsorbent, Li-LSX (lithium-type low-silica X-type zeolite molecular sieve) shows good air separation yield, Li-LSX has high N2 adsorption capacity and high N 2 / O 2 selectivity, which is due to the presence of O in the lithium-containing molecular sieve channel 2 Compared to (-1.4 D for N2 and -0.4 D for O2), N 2 The quadrupole moment of Li-LSX is larger, resulting in a stronger interaction, but due to the fixed structure of X-type molecular sieves with Si, O and Al as the main framework, the O of Li-LSX 2 Production efficiency has reached its limit and it is difficult to break through (J. J. Potoff, J. I. Siepmann, AlChE J.2001, 47, 1676.)
Jeffrey R. Long (E. D. Bloch, L. J. Murray, W. L. Queen, S. Chavan, S. N. Maximoff, J. P. Bigi, R. Krishna, V. K. Peterson, F. Grandjean, G. J. Long, B. Smit, S. Bordiga, C. M. Brown, J. R. Long, J. Am. Chem. Soc.2011, 133, 14814; b) L. J. Murray, M. Dinca, J. Yano, S. Chavan, S. Bordiga, C. M. Brown, J. R. Long, J. Am. Chem. Soc . 2010, 132, 7856.) etc. proposed some realizations O 2 highly selective adsorption method, these porous materials adsorb O 2 than N 2 stronger, which is mainly due to the combination of low-valent metal centers (such as Cr(II) and Fe(II)) with O 2 A strong O 2 Binding affinity, but in order to achieve high purity oxygen, it needs to be regenerated by additional desorption or heating, so it consumes a lot of energy

Method used

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  • Application of MOF separation material in N2/O2 separation
  • Application of MOF separation material in N2/O2 separation
  • Application of MOF separation material in N2/O2 separation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] MSK-96Cr preparation:

[0034] Metallic chromium powder (104 mg, 2 mmol) and H3BTC (280 mg, 1.34 mmol) were added to a 50 mL polytetrafluoroethylene reactor, and then, 10 mL of methanol / water mixed solution (1:1, v / v ) and 0.8 mL of hydrofluoric acid (4 mmol)) were added to the reaction kettle using a pipette. The above mixture was stirred at 298 K for 0.5 h. After the stirring was completed, the polytetrafluoroethylene reactor was sealed in a stainless steel shell and placed in an oven. The temperature of the oven was raised from room temperature to 483 K within 12 h, and kept at 483 K for 96 h, and then the reactor was taken out to cool down to room temperature naturally. The light green product obtained by the reaction was first filtered, and then washed three times with distilled water and methanol at a ratio of 1 g product / 250 mL distilled water and 1 g product / 250 mL methanol at 353 K to remove excess unreacted organic compounds. body. The resulting MSK-96Cr pr...

Embodiment 2

[0043] Example 2 N at different pressures 2 Adsorption capacity

[0044] Different adsorbent materials MIL-100Cr, ZIF-8, UIO-66, Co-MOF-74, Cu-BTC, MIL-101Cr, 13X, Li-LSX and MSK-96Cr materials were mixed at 298 K with a gas flow rate of 15ml / min, N 2 Different N with partial pressure of 0.1 bar, 0.5 bar, 0.79 bar, 1 bar 2 / O 2 Mixed gas to N 2 For the comparison of separation capacity, the equipment used for gas adsorption is the same as that of Example 1.

[0045] according to Figure 4 The results shown, combined with the respective adsorption materials for N 2 It can be seen from the adsorption situation that MSK-96Cr exhibits the highest N 2 Adsorption capacity, N at 1 bar 2 The adsorption capacity can reach 37.46 cm 3 •cm -3 , the adsorption capacity is remarkable.

Embodiment 3

[0046] Example 3 Adsorption selectivity Different adsorption materials MIL-100Cr, ZIF-8, UIO-66, Co-MOF-74, Cu-BTC, MIL-101Cr, 13X, Li-LSX and MSK-96Cr were used for the above samples Carry out gas adsorption experiment, the equipment used of gas adsorption is the same as embodiment 1.

[0047] At 298K and 1 bar, N 2 N at partial pressures of 0.01 bar, 0.1 bar, 0.50 bar and 0.79 bar 2 / O 2 (total pressure is 1bar) mixed gas to N 2 Selective results such as Figure 5 and Table 1.

[0048] Table 1 N of different adsorbents 2 / O 2 selectivity

[0049]

[0050]

[0051] The results show that MSK-96Cr has better adsorption selectivity than other adsorbent materials under several partial pressure conditions.

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Abstract

The invention discloses an application of an MOF separation material in N2/O2 separation. The N2/O2 separation is an important method for producing high-purity O2. According to the invention, a chromium-based metal organic framework material, namely MSK-96Cr, is adopted, the N2 adsorption capacity of the material is 37.46 cm<3>cm<-3>, and the N2/O2 (10: 90, v/v) selectivity is 22.45 (at 298 K and 1 bar). The MSK-96Cr has high N2 adsorption capacity, so that the gas adsorption equilibrium time is also remarkably shortened; meanwhile, N2 is preferentially adsorbed by means of unsaturated Cr metal sites, high-selectivity N2 adsorption can be realized in different N2/O2 (50/50-79/21, v/v) concentration ranges, particularly, the N2 adsorption capacity is higher than that of other adsorption materials under a relatively high oxygen concentration, the separation efficiency is 153 mmol/L under a simulated air component N2/O2 (79/21, v/v), and good oxygen production efficiency is achieved; and the material has a huge application value for industrial production of high-purity oxygen.

Description

technical field [0001] The invention relates to the field of metal organic framework materials, in particular to a kind of MOF separation material in N 2 / O 2 applications in separation. Background technique [0002] High-purity oxygen (>99%) is one of the most widely used commodity chemicals in the world, for example in medical, military, aerospace, semiconductor industries and plasma chemical applications. Currently, air separation is the main method for producing high-purity O 2 The most direct method, mainly adopts low-temperature distillation technology with high energy consumption and large investment cost, and only relies on N 2 (77.15 K) and O 2 (90.15 K) boiling point difference. Although cryogenic distillation is a proven technology for large-scale air separation (>100 tons / year), for medium-volume or portable oxygen supply, it is more economical and flexible to use membrane or adsorption separation processes for air separation. [0003] Temperature / Pre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J20/22B01D53/02B01J20/30
CPCB01J20/226B01D53/02B01D2257/102B01D2256/12
Inventor 夏祖良
Owner 郑州密斯卡化工科技有限公司
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