硝酸镁改性碳分子筛分离氮气/甲烷的性能研究

doi:10.19964/j.issn.1006-4990.2022-0639

Abstract

Abstract:

Modified carbon molecular sieve is an excellent porous adsorbent，which is mostly used in fields such as air separation and nitrogen production.However，the development of adsorbents restricts the application range of pressure swing adsorption process，and excellent adsorbents require superior separation performance.A series of modified CMS were prepared by equal volume impregnation method with magnesium nitrate as modifier based on industrial CMS.The adsorption characteristics of methane and nitrogen on these adsorbents were measured by the volumetric method under PSA process conditions（303 K，0~0.7 MPa，200 s）.The adsorption isotherm experimental data and kinetic curve data were fitted by using the Sips model and the LDF model，respectively，and the separation performance and adsorption characteristic parameters were obtained.The results showed that the modified carbon molecular sieves treatment reduced the specific surface area，micropore volume and average pore size of CMS，while making the pore size distribution more concentrated.The modified CMS with narrow pore size distribution exhibited better nitrogen selectivity owing to regulating the pore size distribution of CMS，and the excellent CMS-0.5 sample had a separation ratio of 12.20 at 303 K and 0.4 MPa.

Key words: carbon molecular sieve modified, adsorption, magnesium nitrate, kinetic separation

CLC Number:

TQ127.1

ZHOU Shiqi, WANG Tao, JING Fangli, LUO Shizhong. Study on performance of magnesium nitrate-modified carbon molecular sieve for separation of nitrogen/methane[J]. Inorganic Chemicals Industry, 2023, 55(9): 75-80.

Figures/Tables 8

Fig.1

Table 1

Fig.2

Fig.3

Fig.4

Table 2

Fitting parameters of Sips model of nitrogen and methane adsorption equilibrium on magnesium nitrate-modified CMS at 303 K"

吸附剂	N₂				CH₄
吸附剂	$q m$ / （mL·g^-1）	$K$ / （MPa^-1）	n	R²	$q m$ / （mL·g^-1）	$K$ /（MPa^-1）	n	R²
CMS	30.99	2.01	0.78	0.999	83.06	1.21	0.53	0.999
CMS-0.1	30.86	2.04	0.78	0.998	57.40	1.25	0.41	0.999
CMS-0.3	29.27	2.13	0.72	0.998	31.07	1.12	0.31	0.998
CMS-0.5	27.63	2.15	0.71	0.997	13.20	1.10	0.33	0.985

Table 2

Table 3

Fitting parameters of LDF model of nitrogen and methane adsorption kinetics plots over modified CMS at 303 K"

吸附剂	N₂			CH₄
吸附剂	$k L$ / （×10^-2s^-1）	$D e / r 2$ / （×10^-3s^-1）	R²	$k L$ / （×10^-4s^-1）	$D e / r 2$ / （×10^-5s^-1）	R²
CMS	2.04	1.36	0.981	2.74	1.83	0.999
CMS-0.1	1.84	1.22	0.993	2.18	1.45	0.999
CMS-0.3	1.43	0.95	0.979	1.83	1.22	0.999
CMS-0.5	0.49	0.04	0.980	0.74	0.05	0.997

Table 3

Fig.5

References 20

1	International Energy Outlook-U.S.Energy Information Administration（EIA）［EB/OL］.［2022-2-11］..
2	NOCITO F， DIBENEDETTO A.Atmospheric CO₂ mitigation technologies：Carbon capture utilization and storage［J］.Current Opinion in Green and Sustainable Chemistry，2020，21：34-43.
3	CARREON M A.Molecular sieve membranes for N₂/CH₄ separation［J］.Journal of Materials Research，2018，33（1）：32-43.
4	ABD A A， OTHMAN M R， NAJI S Z，et al.Methane enrichment in biogas mixture using pressure swing adsorption：Process fundamental and design parameters［J］.Materials Today Sustainability，2021，11/12：100063.
5	SKARSTROM C W.Method and apparatus for fractionating gaseous mixtures by adsorption. US，2944627［P］.1960-2-12.
6	GOLMAKANI A， FATEMI S， TAMNANLOO J.CO₂ capture from the tail gas of hydrogen purification unit by vacuum swing adsorption process，using SAPO-34［J］.Industrial & Engineering Chemistry Research，2016，55（1）：334-350.
7	XIAO Gongkui， LI Zhikao， SALEMAN T L，et al.Adsorption equilibria and kinetics of CH₄ and N₂ on commercial zeolites and carbons［J］.Adsorption，2017，23（1）：131-147.
8	BAE Y S， MOON J H，AHN H，et al.Effects of adsorbate properties on adsorption mechanism in a carbon molecular sieve［J］.Korean Journal of Chemical Engineering，2004，21（3）：712-720.
9	LUO Jingjie， LIU Yuefeng， JIANG Chengfa，et al.Experimental and modeling study of methane adsorption on activated carbon derived from anthracite［J］.Journal of Chemical & Engineering Data，2011，56（12）：4919-4926.
10	YU H J， SHIN J H， LEE A S，et al.Tailoring selective pores of carbon molecular sieve membranes towards enhanced N₂/CH₄ separation efficiency［J］.Journal of Membrane Science，2021，620：118814.
11	XU Shuang， LI Wencui， WANG Chengtong，et al.Self-pillared ultramicroporous carbon nanoplates for selective separation of CH₄/N₂ ［J］.Angewandte Chemie International Edition，2021，60（12）：6339-6343.
12	ZHANG Shichao， CHEN Wenbin， MU Junju，et al.Single siteNi（Ⅱ） anchored tetraethylene pentamine for enhancing CO₂ kinetic adsorption rate and long-term cyclic stability［J］.Chemical Engineering Journal，2022，436：135211.
13	PEREDO-MANCILLA D， GHIMBEU C M， RÉTY B，et al.Surface-modified activated carbon with a superior CH₄/CO₂ adsorption selectivity for the biogas upgrading process［J］.Industrial & Engineering Chemistry Research，2022，61（34）：12710-12727.
14	DO D D.Adsorption Analysis：Equilibria and kinetics［M］.London：World scientific publishing Co.Pte.Ltd，1998.
15	SIPS R.On the structure of a catalyst surface［J］.The Journal of Chemical Physics，1948，16（5）：490-495.
16	WANG Jianlong， GUO Xuan.Adsorption kinetic models：Physical meanings，applications，and solving methods［J］.Journal of Hazardous Materials，2020，390：122156.
17	RUTHVEN D M.Principles of adsorption and adsorption processes［M］.New York：Wiley，1984.
18	SONWANE C G， BHATIA S K.Characterization of pore size distributions of mesoporous materials from adsorption isotherms［J］.The Journal of Physical Chemistry B，2000，104（39）：9099-9110.
19	REID C R， THOMAS K M.Adsorption of gases on a carbon molecular sieve used for air separation：Linear adsorptives as probes for kinetic selectivity［J］.Langmuir，1999，15（9）：3206-3218.
20	ZHANG Jinhua， QU Sijian， LI Lanting，et al.Preparation of carbon molecular sieves used for CH₄/N₂ separation［J］.Journal of Chemical & Engineering Data，2018，63（5）：1737-1744.

样品	比表面积/ （m²·g^-1）	微孔体积/ （cm³·g^-1）	平均孔径/ nm
CMS	525.1	0.112	0.637 5
CMS-0.1	513.6	0.111	0.636 3
CMS-0.3	489.4	0.109	0.635 6
CMS-0.5	468.8	0.105	0.635 3

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Study on performance of magnesium nitrate-modified carbon molecular sieve for separation of nitrogen/methane

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