真空变温吸附捕集干烟道气中CO2的模拟研究

doi:10.11949/0438-1157.20190725

摘要/Abstract

摘要：

为减缓气候变化，减少CO₂的排放，对真空变温吸附(TVSA)从干烟道气中捕集CO₂进行了系统的研究。以沸石13X为吸附剂，设计了实验室规模的4塔连续进料的TVSA工艺，并建立数学模型进行数值模拟。模拟结果表明，通过四塔TVSA可获得纯度为97.54%，回收率为96.79%的CO₂产品气，其产率为1.7 mol· $(k g ? a d s)$ ^-1·h^-1，能耗为3.14 $M J · (k g ? C O 2) - 1$ 。此外，考察了进料量、循环回流步骤时间、真空度对产品气纯度、回收率、吸附剂产率和工艺能耗的影响，并且分析了塔内压力与温度变化，详细探讨了塔内气固相浓度随轴向的分布。良好的工艺效果表明，TVSA有潜力成为一种能够生产高纯度高回收率的CO₂产品气，并具有良好经济效益的捕碳工艺。

关键词: 烟道气, CO₂, 真空变温吸附, 13X, 模拟

Abstract:

To mitigate climate change and reduce CO₂ emissions, a systematic study on the capture of CO₂ from dry flue gas by temperature vacuum swing adsorption (TVSA) was conducted. With zeolite 13X as adsorbent, a four-bed TVSA with continuous feeding was designed, and a mathematical model was established for numerical simulation. Results showed that with the productivity of 1.7 mol·(kg ads)^-1·h^-1 and energy consumption of 3.14 MJ· $(k g ? C O 2) - 1$ _,, CO₂ purity of 97.54% and CO₂ recovery of 96.79% can be obtained by the four-bed TVSA process. The effect of feed flowrate, recycle time and vacuum level on purity, recovery, productivity and energy consumption was investigated. Additionally, the pressure and temperature behaviors in the column were analyzed, and the distribution of gas phase and adsorbed phase concentration in the axial direction was discussed in detail. The good performance indicated that TVSA will have the potential to be a cost-effective process capable of producing high purity and high recovery CO₂ product.

Key words: flue gas, CO₂, temperature vacuum swing adsorption, 13X, simulation

中图分类号:

TQ 028.1

江南, 刘冰, 唐忠利, 张东辉, 李国兵. 真空变温吸附捕集干烟道气中CO₂的模拟研究[J]. 化工学报, 2019, 70(10): 4032-4042.

Nan JIANG, Bing LIU, Zhongli TANG, Donghui ZHANG, Guobing LI. Simulation study on CO₂ capture from dry flue gas by temperature vacuum swing adsorption[J]. CIESC Journal, 2019, 70(10): 4032-4042.

图/表 16

图1 TVSA循环工艺示意图

Fig.1 Process schematic diagram for TVSA cycle

图2 四塔TVSA工艺整体结构

Fig.2 Configuration of four-bed TVSA process

表1 TVSA工艺时序

Table 1 Cycle sequence of TVSA process

Bed	Time/s
Bed	200	200	600	200	200	600	200	200	600	200	200	600
1	AD			RE	H			VU	C	C&PR
2	C&PR			AD			RE	H			VU	C
3	H	VU	C	C&PR			AD			RE	H
4	RE	H			VU	C	C&PR			AD

表2 吸附床的模型方程

Table 2 Model equations of adsorption bed

	模型方程
质量平衡	$- ε b D a x, i ? 2 c i ? z 2 + ? v g c i ? z + [ε b + 1 - ε b ε p] ? c i ? t + ρ s 1 - ε b ? q i ? t = 0$ $D a x, i = 0.73 D m, i + v g r p ε b 1 + 9.49 ε b D m, i 2 v g r p$ , $D m = 0.1013 T 1.75 1 M A + 1 M B P (D v, A 13 + D v, B 13) 2$
热量平衡	气相： $- k g ε b ? 2 T g ? z 2 + C v g v g ρ g ? T g ? z + ε b C v g ρ g ? T g ? t + P ? v g ? z + h f α p T g - T s + 4 h w D b (T g - T 0) = 0$
	固相： $- k s ? 2 T s ? z 2 + C p s ρ b ? T s ? t + ρ b ∑ i = 1 n (C p a, i w i) ? T s ? t + ρ b ∑ i = 1 n (? H i ? q i ? t) - h f α p T g - T s = 0$
	塔壁： $? - k w ? 2 T w ? z 2 + C p w ρ w ? T g ? z - h w 4 D b (D b + W t) 2 - D b 2 T g - T w + h m α H X T w - T m = 0$
	冷/热流体相： $- k m ? 2 T m ? z 2 + C v m v m ρ m ? T m ? z + C v m ρ m ? T m ? t + h m α H X T w - T m$
动量平衡	$- ? P ? z = 150 μ 1 - ε b 2 ε b 3 2 r p ψ 2 v g + 1.75 M 1 - ε b ρ g 2 r p ψ ε b 3 v g v g$
线性推动力	$? q i ? t = k L D F, i q i * - q i$
吸附平衡	$q i * = I P 1 i e I P 2 i T P i 1 + ∑ i = 1 n I P 3 i e I P 4 i T P i$
纯度	$p u r i t y = ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, i d t ∫ 0 t c y c l e F p r o d u c t d t × 100 %$
回收率	$r e c o v e r y ∫ 0 t c y c l e F p r o d u c t, i y p r o d u c t, i d t ∫ 0 t c y c l e F f e e d, i y f e e d, c o d t$ $× 100 %$
产率	$3600 (∫ 0 t c y c l e F p r o d u c t, i y p r o d u c t, i d t) t c y c l e w a d s$
能耗	$∫ 0 t c y c l e F f e e d P f e e d γ η γ - 1 P f e e d P a t m 1 - 1 γ - 1 d t ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t + ∫ 0 t c y c l e F v a c P v a c γ η γ - 1 P f e e d P a t m 1 - 1 γ - 1 d t ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t + C p w T H - T L V w a l l ρ w + [C p s T H - T L - ρ b ∑ i = 1 2 Δ n i - Δ H i] V c o l ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t$

表2 吸附床的模型方程

Table 2 Model equations of adsorption bed

	模型方程
质量平衡	$- ε b D a x, i ? 2 c i ? z 2 + ? v g c i ? z + [ε b + 1 - ε b ε p] ? c i ? t + ρ s 1 - ε b ? q i ? t = 0$ $D a x, i = 0.73 D m, i + v g r p ε b 1 + 9.49 ε b D m, i 2 v g r p$ , $D m = 0.1013 T 1.75 1 M A + 1 M B P (D v, A 13 + D v, B 13) 2$
热量平衡	气相： $- k g ε b ? 2 T g ? z 2 + C v g v g ρ g ? T g ? z + ε b C v g ρ g ? T g ? t + P ? v g ? z + h f α p T g - T s + 4 h w D b (T g - T 0) = 0$
	固相： $- k s ? 2 T s ? z 2 + C p s ρ b ? T s ? t + ρ b ∑ i = 1 n (C p a, i w i) ? T s ? t + ρ b ∑ i = 1 n (? H i ? q i ? t) - h f α p T g - T s = 0$
	塔壁： $? - k w ? 2 T w ? z 2 + C p w ρ w ? T g ? z - h w 4 D b (D b + W t) 2 - D b 2 T g - T w + h m α H X T w - T m = 0$
	冷/热流体相： $- k m ? 2 T m ? z 2 + C v m v m ρ m ? T m ? z + C v m ρ m ? T m ? t + h m α H X T w - T m$
动量平衡	$- ? P ? z = 150 μ 1 - ε b 2 ε b 3 2 r p ψ 2 v g + 1.75 M 1 - ε b ρ g 2 r p ψ ε b 3 v g v g$
线性推动力	$? q i ? t = k L D F, i q i * - q i$
吸附平衡	$q i * = I P 1 i e I P 2 i T P i 1 + ∑ i = 1 n I P 3 i e I P 4 i T P i$
纯度	$p u r i t y = ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, i d t ∫ 0 t c y c l e F p r o d u c t d t × 100 %$
回收率	$r e c o v e r y ∫ 0 t c y c l e F p r o d u c t, i y p r o d u c t, i d t ∫ 0 t c y c l e F f e e d, i y f e e d, c o d t$ $× 100 %$
产率	$3600 (∫ 0 t c y c l e F p r o d u c t, i y p r o d u c t, i d t) t c y c l e w a d s$
能耗	$∫ 0 t c y c l e F f e e d P f e e d γ η γ - 1 P f e e d P a t m 1 - 1 γ - 1 d t ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t + ∫ 0 t c y c l e F v a c P v a c γ η γ - 1 P f e e d P a t m 1 - 1 γ - 1 d t ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t + C p w T H - T L V w a l l ρ w + [C p s T H - T L - ρ b ∑ i = 1 2 Δ n i - Δ H i] V c o l ∫ 0 t c y c l e F p r o d u c t y p r o d u c t, C O 2 d t$

表3 吸附床和吸附剂的物性参数

Table 3 Physical characteristics of adsorption bed and sorbent

参数	数值
H _b/m	1
D _b/m	0.1
W _t/m	0.005
ε _b	0.38
ε _p	0.384
ψ	0.91
ρ _b/(kg?m^-3)	756
ρ _w/(kg?m^-3)	7800
r _p/m	9×10^-4
C_p _s/(kJ?kg^-1?K^-1)	0.504
C_p _w/(kJ?kg^-1?K^-1)	0.52
h _w/(W?m^-2?K^-1)	220
$k L D F, C O 2$	0.1
$k L D F, N 2$	0.5

表3 吸附床和吸附剂的物性参数

Table 3 Physical characteristics of adsorption bed and sorbent

参数	数值
H _b/m	1
D _b/m	0.1
W _t/m	0.005
ε _b	0.38
ε _p	0.384
ψ	0.91
ρ _b/(kg?m^-3)	756
ρ _w/(kg?m^-3)	7800
r _p/m	9×10^-4
C_p _s/(kJ?kg^-1?K^-1)	0.504
C_p _w/(kJ?kg^-1?K^-1)	0.52
h _w/(W?m^-2?K^-1)	220
$k L D F, C O 2$	0.1
$k L D F, N 2$	0.5

表4 工艺操作参数

Table 4 Process operating parameters

参数	数值
T _f/K	298.15
P _a/Pa	1.5×10⁵
T _heat/K	413.15
T _cool/K	298.15

图3 不同温度下CO2和N2在13X上的吸附等温线

Fig.3 Adsorption isotherms of CO2 and N2 on 13X at different temperature

表5 拓展的Langmuir吸附等温线参数

Table 5 Adsorptin isotherm parameters fitted by extended Langmuir model

Item

IP₁/(kmol·kg^-1·bar^-1)

IP₂/K

IP₃/bar^-1

IP₄/K

ΔH/

(kJ·mol^-1)

CO₂

N₂

图4 TVSA工艺的能耗分布

Fig.4 Energy consumption distribution of TVSA process

图5 TVSA工艺单周期压力图

Fig.5 Pressure profile of TVSA process over one cycle

图6 TVSA工艺单周期塔内温度沿轴向分布

Fig.6 Temperature distribution within adsorption column over one cycle in TVSA process

图7 进料量对工艺效果的影响

Fig.7 Effects of feed flowrate on process performance

图8 循环回流时间对工艺效果的影响

Fig.8 Effects of recycle time on process performance

图9 真空度对工艺效果的影响

Fig.9 Effects of vacuum pressure on process performance

图10 塔内CO2和N2固相浓度分布

Fig.10 Adsorbed phase concentration of CO2 and N2 within adsorption column

图11 塔内CO2和N2气相浓度分布

Fig.11 Gas phase concentration of CO2 and N2 within adsorption column

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真空变温吸附捕集干烟道气中CO₂的模拟研究

Simulation study on CO₂ capture from dry flue gas by temperature vacuum swing adsorption

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