电子级HF吸附法回收的节能降耗潜力分析

doi:10.16085/j.issn.1000-6613.2020-1721

摘要/Abstract

摘要：

电子级氟化氢（HF）气体的回收具有良好的经济、环境、社会效益，吸附法是最有希望实现回收的方式之一。然而能耗问题限制其进一步发展，如何对其展开节能降耗尚未见专题研究。本文通过对吸附循环能耗等指标的计算，对吸附循环的性能展开了探索性研究。采用分子模拟技术，计算获得HF的吸附平衡等温线数据；建立变温吸附循环数值模型，明确评价循环效能的指标参数；改变吸附温度、压力等运行参数，分析能耗、能效等循环指标的变化趋势，探索降低能耗提升效率的方向。计算结果表明：吸附温度由298K降低到288K，回收单位质量HF能耗由14.0912MJ/kg降低为3.1173MJ/kg，能量利用效率由0.02升高到0.0953；解吸温度由340K升高到350K，能耗降低为12.0037MJ/kg，能量利用效率升高到0.0247。可以看出，降低吸附温度对降低能耗、提升能效的作用更加明显。此外，还得到以下结论：提高进气浓度对各指标均有积极影响；提高吸附压力仅对回收率有较大影响；冷热源与操作温度的差值仅影响产率大小。

关键词: 氟化氢, 分子模拟, 回收, 解吸，脱附, 能耗, 变温吸附

Abstract:

The recovery of electronic-grade hydrogen fluoride (HF) gas has good economic, environmental and social benefits, and adsorption is one of the most promising methods for its recycling. However, the problem of high energy requirement limits its further development, and the research on the energy conservation and consumption reduction has not been conducted for this process. The performance of the adsorption cycle was studied by calculating a series of indexes such as energy consumption. The adsorption equilibrium isotherm data of HF was calculated by molecular simulation technique. The numerical model of temperature swing adsorption (TSA) was established, which was used to determine the index parameters of evaluation cycle efficiency. The operating parameters such as adsorption temperature and pressure were changed to analyze the changing trends of the cycle indicators such as energy consumption and energy efficiency, so as to explore the direction of reducing energy consumption and improving efficiency. The results showed that when the adsorption temperature decreased from 298K to 288K, the recycling energy consumption reduced from 14.0912MJ/kg to 3.1173MJ/kg HF, and the energy utilization efficiency increased from 0.02 to 0.0953. Moreover, as the desorption temperature increased from 340K to 350K, the recycling energy consumption reduced from14.0912MJ/kg to 12.0037MJ/kg HF, and the energy utilization efficiency increased from 0.02 to 0.0247. These results indicated that reducing the adsorption temperature is more significant in reducing energy consumption and improving energy efficiency. In addition, the following conclusions were also obtained: increasing intake concentration had positive effects on all the indexes while the increase of adsorption pressure only had a great influence on the recovery rate. The temperature difference between hot and cold sources and operation only affected the yield.

Key words: hydrogen fluoride (HF), molecular simulation, recovery, desorption, energy consumption, temperature swing adsorption

中图分类号:

O647.3

王傢俊, 邓帅, 赵睿恺, 赵力. 电子级HF吸附法回收的节能降耗潜力分析[J]. 化工进展, 2021, 40(7): 3645-3655.

WANG Jiajun, DENG Shuai, ZHAO Ruikai, ZHAO Li. Analysis of energy and consumption reduction in adsorption recovery of electronic HF[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3645-3655.

图/表 25

图1 文献涉及HF吸附实验结果

图2 研究方法流程图

表1 Cu-BTC和HF的力场参数

原子名称	$ε / k B / K$	σ/?	电荷（e^-）
Cu	2.516	3.11	1.248
O	48.158	3.03	-0.624
C1	47.856	3.47	0.494
C2	47.856	3.47	0.13
C3	47.856	3.47	-0.156
H	7.65	2.85	0.156
F_ hf	60.0	2.830	0.592
H_ hf	0	0	0.592
HF_ w	0	0	-1.184

表1 Cu-BTC和HF的力场参数

原子名称	$ε / k B / K$	σ/?	电荷（e^-）
Cu	2.516	3.11	1.248
O	48.158	3.03	-0.624
C1	47.856	3.47	0.494
C2	47.856	3.47	0.13
C3	47.856	3.47	-0.156
H	7.65	2.85	0.156
F_ hf	60.0	2.830	0.592
H_ hf	0	0	0.592
HF_ w	0	0	-1.184

表2 HF的原子几何参数

键的形式	键的长度/?
F—H	0.973
F—X	0.1647

表3 温度和压力的数值

个数	测试温度/K	测试压力/Pa
1	298	1000
2	300	10000
3	313	20000
4	330	50000
5	340	70000
6	360	—
7	380	—
8	400	—
9	420	—

图3 Cu-BTC对于HF的吸附模拟结果

表4 相关吸附平衡等温线模型

吸附平衡等温线模型	模型表达式	模型参数表达式
Langmuir模型	$q = q K m p 1 + K p$	$K = K 0 e x p Q R T$	$q m = a T + b$
Toth模型	$q = q m K p [1 + (K p) d] (1 / d)$	$K = K 0 e x p Q R T$	$d = d 0 + α 1 - T 0 T$
Sips模型	$q = q m ? (K p) c 1 + (K p) c$	$K = K 0 e x p Q R T$	$c = c 0 + α T T 0 - 1$

表4 相关吸附平衡等温线模型

吸附平衡等温线模型	模型表达式	模型参数表达式
Langmuir模型	$q = q K m p 1 + K p$	$K = K 0 e x p Q R T$	$q m = a T + b$
Toth模型	$q = q m K p [1 + (K p) d] (1 / d)$	$K = K 0 e x p Q R T$	$d = d 0 + α 1 - T 0 T$
Sips模型	$q = q m ? (K p) c 1 + (K p) c$	$K = K 0 e x p Q R T$	$c = c 0 + α T T 0 - 1$

图4 TSA操作的4个步骤

图5 应用于电子级HF回收的混合气体分离模型示意图

表5 吸附腔相关的参数

参数	数值
管壳内管几何尺（d_i）/cm	3
管壳外管几何尺（d_o）/cm	3.18
比换热面积（S）/m2·m-3	133.5
总换热热阻（U）/J·m-2·K-1	16.8
不锈钢壁面比热容（c_p_w）/J·m-3·K-1	4000000
进料速度（y_F）/m·s-1	0.5
环境压力（p_H）/Pa	1.01×10⁵
吸附床床长（L）/m	1.2

表6 298K时吸附平衡等温线的拟合结果

吸附平衡等温线模型	R²
Langmuir模型	0.8286
Toth模型	0.7734
Sips模型	0.9987

表7 Sips模型温度相关形式的拟合结果

表达式参数	参数数值	R²
$q m$	300	0.9764
K₀	7.159
Q	-10420
c₀	1.748
α	17.26

表7 Sips模型温度相关形式的拟合结果

表达式参数	参数数值	R²
$q m$	300	0.9764
K₀	7.159
Q	-10420
c₀	1.748
α	17.26

图6 不同TH对Pr、eth的影响

图7 不同TH对QTSA、r的影响

图8 不同TH对η、Wmin的影响

图9 不同TL对Pr、eth的影响

图10 不同TL对QTSA、r的影响

图11 不同TL对Wmin、η的影响

图12 不同yin对Pr、eth的影响

图13 不同yin对QTSA、r的影响

图14 不同yin对Wmin、η的影响

图15 不同压力对Pr、eth的影响

图16 不同压力对QTSA、r的影响

图17 不同压力对Wmin、η的影响

图18 不同冷热源温度对Pr的影响

参考文献 21

1	洪海江, 应振洲, 余锋, 等. 电子级氢氟酸的纯化技术及其配套技术[J]. 有机氟工业, 2012(3): 25-29.
	HONG Haijiang, YING Zhenzhou, YU Feng, et al. Purification technology for electronic-grade hydrofluoric acid and its associated technology[J]. Organic Forine Istry, 2012(3): 25-29.
2	李丹丹, 岳立平, 郑艺. 无水氟化氢的纯化工艺研究进展[J]. 化学工程师, 2017, 31(9): 36-37, 39.
	LI Dandan, YUE Liping, ZHENG Yi. Advances in purification study of fluoride hydrogen[J]. Chemical Engineer, 2017, 31(9): 36-37, 39.
3	金正义, 应学来. 含氟化学品生产中过量氟化氢的吸附回收技术[J]. 有机氟工业, 2007(3): 28-29, 33.
	JIN Zhengyi, YING Xuelai. The adsorption and recovery technology of excessive hydrogen fluoride in the production of fluorinated chemicals[J]. Organic Fluorine Industry, 2007(3): 28-29, 33.
4	刘飞, 邱祖军, 尹峰, 等. 电子级氢氟酸的纯化技术及其发展现状[J]. 硫磷设计与粉体工程, 2012(1): 44-48.
	LIU Fei, QIU Zujun, YIN Feng, et al. Purification technology of electron-grade hydrofluoric acid and its development status[J]. Design and Powder Engineering of Sulfur-Phosphorus, 2012(1): 44-48.
5	王文利, 白志民. 中国萤石资源及产业发展现状[J]. 金属矿山, 2014(3): 1-9.
	WANG Wenli, BAI Zhimin. Current situation of fluorite resources and industry development in China[J]. Metal Mine, 2014(3): 1-9.
6	李敬, 高永璋, 张浩. 中国萤石资源现状及可持续发展对策[J]. 中国矿业, 2017, 26(10): 7-14.
	LI Jing, GAO Yongzhang, ZHANG Hao.Current situation and sustainable development countermeasures of fluorite resources in China[J]. China Mining, 2017, 26(10): 7-14.
7	贾磊. 日本限制对韩氟化氢出口[J]. 无机盐工业, 2019, 51(8): 94.
	JIA L. Restriction of export of hydrogen fluoride to Korea by Japan[J]. Inorfanic Chemicals Industry, 2019, 51(8): 94.
8	AFZAL S, RAHIMI A, EHSANI M R, et al. Experimental study of hydrogen fluoride adsorption on sodium fluoride[J]. Journal of Industrial & Engineering Chemistry, 2010, 16(1):147-151.
9	SIAHOOEI M A, BORDBARI K. Adsorption of fluoride gases in aluminum production by using of nanotechnology[M]. Berlin: Springer International Publishing, 2019: 121-136.
10	WANG C, LIU B, SUN F, et al. New challenge of microporous metal-organic frameworks for adsorption of hydrogen fluoride gas[J]. Materials Letters, 2017, 197: 175-179.
11	BAHRAMI H, SAFDARI J, MOOSAVIAN M A, et al. Adsorption of hydrogen fluoride onto activated carbon under vacuum conditions: equilibrium, kinetic and thermodynamic investigations[J]. Chemical Industry and Chemical Engineering Quarterly, 2012, 18(4): 497-508.
12	CASTILLO J M, VLUGT T J H, CALERO, et al. Understanding water adsorption in Cu-BTC Metal-Organic frameworks[J]. Journal of Physical Chemistry C, 2008, 112(41): 15934-15939.
13	PARTAY L B, JEDLOVSZKY P, HOANG P N M, et al. Free-energy profile of small solute molecules at the free surfaces of water and ice, as determined by cavity insertion widom calculations[J]. Journal of Physical Chemistry C, 2007, 111(26): 9407-9416.
14	ZHAO R, ZHAO L, DENG S, et al. A comparative study on CO₂ capture performance of vacuum-pressure swing adsorption and pressure-temperature swing adsorption based on carbon pump cycle[J]. Energy, 2017, 137: 495-509.
15	DU Z, NIE X, DENG S, et al. Comparative analysis of calculation method of adsorption isosteric heat: case study of CO₂ capture using MOFs[J]. Microporous and Mesoporous Materials, 2020, 298: 110053.
16	MAX, HEFTI, DORIAN, et al. Adsorption equilibrium of binary mixtures of carbon dioxide and nitrogen on zeolites ZSM-5 and 13X[J]. Microporous and Mesoporous Materials, 2015, 215: 215-288.
17	JIANG L, ROSKILLY A P, WANG R Z. Performance exploration of temperature swing adsorption technology for carbon dioxide capture[J]. Energy Conversion & Management, 2018, 165: 396-404.
18	KIM Min-Bae, MOON Jong-Ho, LEE Chang-Ha, et al. Effect of heat transfer on the transient dynamics of temperature swing adsorption process[J]. Korean Journal of Chemical Engineering, 2004, 21(3): 73-711.
19	JOSS L, GAZZANI M, HEFTI M, et al. Temperature swing adsorption for the recovery of the heavy component: an equilibrium-based shortcut model[J]. Industrial & Engineering Chemistry Research, 2015, 54(11): 3027-3038.
20	ZHAO R, DENG S, LIU Y, et al. Carbon pump: fundamental theory and applications[J]. Energy, 2017, 119:1131-1143.
21	KLOUTSE F A, ZACHARIA R, COSSEMENT D, et al. Specific heat capacities of MOF-5, Cu-BTC, Fe-BTC, MOF-177 and MIL-53 (Al) over wide temperature ranges: measurements and application of empirical group contribution method[J]. Microporous and Mesoporous Materials, 2015, 217: 1-5.

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