合成氨反应器尾气变压吸附氨分离工艺的模拟与分析

doi:10.11949/0438-1157.20240870

摘要/Abstract

摘要：

氨的分离和回收在工业中有着广泛应用，但传统的氨分离方法往往伴随着较高的能耗。变压吸附技术作为一种低能耗、设备简单、操作灵活的气体分离方式，在气体分离领域有着广泛的应用。目前，对于变压吸附氨分离工艺缺乏详细的分析研究。基于此，以简化的合成氨反应器尾气为研究对象，以实验室自制的高硅铝比分子筛HS-1为吸附剂，测定了NH₃、N₂和H₂三种气体在该吸附剂上的吸附数据，为仿真模拟提供了相关参数。提出了一种两塔真空变压吸附工艺，采用数值模拟的方法研究了针对合成氨反应器尾气的氨分离变压吸附工艺，研究了不同操作条件下工艺分离的性能，探究了操作参数对工艺性能的影响。模拟结果表明，在吸附压力5 bar（1 bar=10⁵ Pa），吸附时间250 s，进料量1.2 mol·min^-1的条件下，该工艺分离得到的NH₃纯度可达89.30%，回收率可达94.67%，分离能耗为38.02 kJ·mol^-1。

关键词: 合成氨, 氨分离, 真空变压吸附, 吸附剂, 数值模拟

Abstract:

Ammonia separation and recovery are widely used in industry, but traditional ammonia separation methods are often accompanied by high energy consumption. Pressure swing adsorption (PSA) technology, as a gas separation method with low energy consumption, simple equipment and flexible operation, has been widely used in the field of gas separation. At present, there is a lack of extensive analysis and research on the ammonia separation process of pressure swing adsorption. Based on this, this paper takes the simplified synthetic ammonia reactor-off gas as the research object, and uses a high silica-aluminium ratio molecular sieve HS-1 made in the laboratory as the adsorbent, and determines the adsorption data of three gases, NH₃, N₂ and H₂, on this adsorbent, which provides the relevant parameters for the simulation. A two-bed vacuum pressure swing adsorption (VPSA) process was proposed, the numerical simulation method was used to study the pressure swing adsorption process for ammonia separation of the ammonia synthesis reactor tail gas. In addition, the performance of process separation under different operating conditions is studied to investigate the effect of operating parameters on process performance. The simulation results show that under the conditions of adsorption pressure of 5 bar (1 bar = 10⁵ Pa), adsorption time of 250 s, and feed amount of 1.2 mol·min^-1, the purity of NH₃ separated by this process can reach 89.30%, the recovery rate can reach 94.67%, and the separation energy consumption is 38.02 kJ·mol^-1.

Key words: synthetic ammonia, ammonia separation, vacuum pressure swing adsorption, adsorbents, numerical simulation

中图分类号:

TQ 028.1

贾晶宇, 孔德齐, 沈圆辉, 张东辉, 李文彬, 唐忠利. 合成氨反应器尾气变压吸附氨分离工艺的模拟与分析[J]. 化工学报, 2025, 76(2): 718-730.

Jingyu JIA, Deqi KONG, Yuanhui SHEN, Donghui ZHANG, Wenbin LI, Zhongli TANG. Simulation and analysis of ammonia separation process by pressure swing adsorption from synthetic ammonia reactor-off gas[J]. CIESC Journal, 2025, 76(2): 718-730.

图/表 23

图1 VPSA工艺流程示意图

Fig.1 VPSA process diagram

图2 VPSA工艺各步骤示意图

Fig.2 Schematic diagram of each step in the VPSA process

表1 VPSA工艺时序

Table 1 VPSA process cycle sequence

Step	Bed 1	Bed 2	Time/s
1	AD	VU	250
2	ED	ER	20
3	CoD	PR	30
4	VU	AD	250
5	ER	ED	20
6	PR	CoD	30

表2 吸附床数学模型

Table 2 The mathematical model of adsorption bed

方程	数学公式
质量守恒方程	$- ε_{b} D_{a x, i} \frac{\partial^{2} c_{i}}{\partial z^{2}} + \frac{\partial (v_{g} c_{i})}{\partial z} + [ε_{b} + (1 - ε_{b}) ε_{p}] \frac{\partial c_{i}}{\partial t} + ρ_{b} \frac{\partial q_{i}}{\partial t} = 0$	(1)
	$\begin{matrix} D_{a x, i} = 0.73 D_{m, i} + \frac{v_{g} r_{p}}{ε_{b} (1 + 9.49 \frac{ε_{b} D_{m, i}}{2 v_{g} r_{p}})} \end{matrix}$	(2)
	$D_{m, i} = \frac{0.0101 T^{1.75} \sqrt[]{\frac{1}{M_{A}} + \frac{1}{M_{B}}}}{P ({D_{v, A}}^{1 / 3} + {D_{v, B}}^{1 / 3})^{2}}$	(3)
能量守恒方程	$\begin{matrix} - k_{g} ε_{b} \frac{\partial^{2} T_{g}}{\partial z^{2}} + C_{v g} v_{g} ρ_{g} \frac{\partial T_{g}}{\partial z} + [ε_{b} + (1 - ε_{b}) ε_{p}] C_{v g} ρ_{g} \frac{\partial T_{g}}{\partial t} + P \frac{\partial v_{g}}{\partial z} + H T C \times a_{p} (T_{g} - T_{s}) + \frac{4 h_{w}}{D_{b}} (T_{g} - T_{w}) = 0 \end{matrix}$	(4)
	$\begin{matrix} - k_{s} \frac{\partial^{2} T_{s}}{\partial z^{2}} + ρ_{b} C_{p s} \frac{\partial T_{s}}{\partial t} + ρ_{b} \sum_{i = 1}^{n} (C_{p g, i} q_{i}) \frac{\partial T_{s}}{\partial t} + ρ_{b} \sum_{i = 1}^{n} (Δ H_{i} \frac{\partial q_{i}}{\partial t}) - H T C \times a_{p} (T_{g} - T_{s}) = 0 \end{matrix}$	(5)
	$\begin{matrix} - k_{w} \frac{\partial^{2} T_{w}}{\partial z^{2}} + C_{p w} ρ_{w} \frac{\partial T_{w}}{\partial t} - h_{w} \frac{4 D_{b}}{{(D_{b} + W_{t})}^{2} - D_{b}^{2}} (T_{g} - T_{w}) + h_{a m b} \frac{4 (D_{b} + W_{t})^{2}}{{(D_{b} + W_{t})}^{2} - D_{b}^{2}} (T_{w} - T_{a m b}) = 0 \end{matrix}$	(6)
动量守恒方程	$\begin{matrix} - \frac{\partial P}{\partial z} = \frac{1.5 \times 10^{- 3} μ (1 - ε_{b})^{2}}{{ε_{b}}^{3} (2 r_{p} {ψ)}^{2}} v_{g} + 1.75 \times 10^{- 5} M \frac{(1 - ε_{b}) ρ_{g}}{2 r_{p} ψ {ε_{b}}^{3}} \| v_{g} \| v_{g} \end{matrix}$	(7)
吸附等温线方程	$\begin{matrix} q_{i}^{*} = \frac{I P_{1 i} I P_{2 i} P_{i}^{I P_{3 i}} e^{I P_{4 i} / T}}{1 + \sum_{i = 1}^{n} (I P_{5 i} P_{i}^{I P_{3 i}} e^{I P_{6 i} / T})} \end{matrix}$	(8)
LDF方程	$\begin{matrix} \frac{\partial q_{i}}{\partial t} = k_{L D F, i} (q_{i}^{*} - q_{i}) \end{matrix}$	(9)

表2 吸附床数学模型

Table 2 The mathematical model of adsorption bed

方程	数学公式
质量守恒方程	$- ε_{b} D_{a x, i} \frac{\partial^{2} c_{i}}{\partial z^{2}} + \frac{\partial (v_{g} c_{i})}{\partial z} + [ε_{b} + (1 - ε_{b}) ε_{p}] \frac{\partial c_{i}}{\partial t} + ρ_{b} \frac{\partial q_{i}}{\partial t} = 0$	(1)
	$\begin{matrix} D_{a x, i} = 0.73 D_{m, i} + \frac{v_{g} r_{p}}{ε_{b} (1 + 9.49 \frac{ε_{b} D_{m, i}}{2 v_{g} r_{p}})} \end{matrix}$	(2)
	$D_{m, i} = \frac{0.0101 T^{1.75} \sqrt[]{\frac{1}{M_{A}} + \frac{1}{M_{B}}}}{P ({D_{v, A}}^{1 / 3} + {D_{v, B}}^{1 / 3})^{2}}$	(3)
能量守恒方程	$\begin{matrix} - k_{g} ε_{b} \frac{\partial^{2} T_{g}}{\partial z^{2}} + C_{v g} v_{g} ρ_{g} \frac{\partial T_{g}}{\partial z} + [ε_{b} + (1 - ε_{b}) ε_{p}] C_{v g} ρ_{g} \frac{\partial T_{g}}{\partial t} + P \frac{\partial v_{g}}{\partial z} + H T C \times a_{p} (T_{g} - T_{s}) + \frac{4 h_{w}}{D_{b}} (T_{g} - T_{w}) = 0 \end{matrix}$	(4)
	$\begin{matrix} - k_{s} \frac{\partial^{2} T_{s}}{\partial z^{2}} + ρ_{b} C_{p s} \frac{\partial T_{s}}{\partial t} + ρ_{b} \sum_{i = 1}^{n} (C_{p g, i} q_{i}) \frac{\partial T_{s}}{\partial t} + ρ_{b} \sum_{i = 1}^{n} (Δ H_{i} \frac{\partial q_{i}}{\partial t}) - H T C \times a_{p} (T_{g} - T_{s}) = 0 \end{matrix}$	(5)
	$\begin{matrix} - k_{w} \frac{\partial^{2} T_{w}}{\partial z^{2}} + C_{p w} ρ_{w} \frac{\partial T_{w}}{\partial t} - h_{w} \frac{4 D_{b}}{{(D_{b} + W_{t})}^{2} - D_{b}^{2}} (T_{g} - T_{w}) + h_{a m b} \frac{4 (D_{b} + W_{t})^{2}}{{(D_{b} + W_{t})}^{2} - D_{b}^{2}} (T_{w} - T_{a m b}) = 0 \end{matrix}$	(6)
动量守恒方程	$\begin{matrix} - \frac{\partial P}{\partial z} = \frac{1.5 \times 10^{- 3} μ (1 - ε_{b})^{2}}{{ε_{b}}^{3} (2 r_{p} {ψ)}^{2}} v_{g} + 1.75 \times 10^{- 5} M \frac{(1 - ε_{b}) ρ_{g}}{2 r_{p} ψ {ε_{b}}^{3}} \| v_{g} \| v_{g} \end{matrix}$	(7)
吸附等温线方程	$\begin{matrix} q_{i}^{*} = \frac{I P_{1 i} I P_{2 i} P_{i}^{I P_{3 i}} e^{I P_{4 i} / T}}{1 + \sum_{i = 1}^{n} (I P_{5 i} P_{i}^{I P_{3 i}} e^{I P_{6 i} / T})} \end{matrix}$	(8)
LDF方程	$\begin{matrix} \frac{\partial q_{i}}{\partial t} = k_{L D F, i} (q_{i}^{*} - q_{i}) \end{matrix}$	(9)

表3 辅助设备数学模型

Table 3 Mathematical model of auxiliary equipment

设备

数学模型

泵

$\begin{matrix} T_{o u t} = T_{i n} (P_{o u t} / P_{i n})^{(γ - 1) / γ} \end{matrix}$

$d W = \frac{P_{i n} V_{i n}}{η_{p}} \frac{γ}{γ - 1} [(P_{o u t} / P_{i n})^{\frac{γ - 1}{γ}} - 1]$

$W = \int_{0}^{t} d W$

(10)

缓冲罐

$\begin{matrix} \frac{\partial n_{i}}{\partial t} = \sum_{i = 1}^{n} F_{i n} y_{i, i n} - \sum_{i = 1}^{n} F_{o u t} y_{i, o u t} \end{matrix}$

$\begin{matrix} \frac{\partial T (\sum_{i = 1}^{n} n_{i} C_{p g, i})}{\partial t} = \sum_{i = 1}^{n} y_{i, i n} C_{p g, i} \sum_{j = 1}^{m} F_{i n, j} T_{i n, j} - \sum_{i = 1}^{n} y_{i, o u t} C_{p g, i} \sum_{j = 1}^{m} F_{o u t, j} T_{o u t, j} \end{matrix}$

(11)

阀门

F = C_{V} (P_{o u t} - P_{i n})

(12)

表3 辅助设备数学模型

Table 3 Mathematical model of auxiliary equipment

设备

数学模型

泵

$\begin{matrix} T_{o u t} = T_{i n} (P_{o u t} / P_{i n})^{(γ - 1) / γ} \end{matrix}$

$d W = \frac{P_{i n} V_{i n}}{η_{p}} \frac{γ}{γ - 1} [(P_{o u t} / P_{i n})^{\frac{γ - 1}{γ}} - 1]$

$W = \int_{0}^{t} d W$

(10)

缓冲罐

$\begin{matrix} \frac{\partial n_{i}}{\partial t} = \sum_{i = 1}^{n} F_{i n} y_{i, i n} - \sum_{i = 1}^{n} F_{o u t} y_{i, o u t} \end{matrix}$

(11)

阀门

F = C_{V} (P_{o u t} - P_{i n})

(12)

表4 工艺性能评价指标

Table 4 Process performance indicator

指标	计算公式
纯度	$P u r i t y_{t a r g e t} = \frac{\int_{0}^{t_{c y c l e}} F_{o u t} y_{o u t, t a r g e t} d t}{\int_{0}^{t_{c y c l e}} F_{o u t} d t}$	(13)
回收率	$R e c o v e r y_{t a r g e t} = \frac{\int_{0}^{t_{c y c l e}} F_{o u t} y_{o u t, t a r g e t} d t}{\int_{0}^{t_{c y c l e}} F_{i n} y_{i n, t a r g e t} d t}$	(14)
能耗	$E n e r g y c o n s u m p t i o n = \frac{\int_{0}^{t_{c y c l e}} \frac{V_{i n} P_{o u t} γ}{η (γ - 1)} [(P_{o u t} / P_{i n})^{1 - (1 / γ)} - 1] d t}{\int_{0}^{t_{c y c l e}} V_{p r o d u c t} y_{p r o d u c t} d t}$	(15)

表4 工艺性能评价指标

Table 4 Process performance indicator

指标	计算公式
纯度	$P u r i t y_{t a r g e t} = \frac{\int_{0}^{t_{c y c l e}} F_{o u t} y_{o u t, t a r g e t} d t}{\int_{0}^{t_{c y c l e}} F_{o u t} d t}$	(13)
回收率	$R e c o v e r y_{t a r g e t} = \frac{\int_{0}^{t_{c y c l e}} F_{o u t} y_{o u t, t a r g e t} d t}{\int_{0}^{t_{c y c l e}} F_{i n} y_{i n, t a r g e t} d t}$	(14)
能耗	$E n e r g y c o n s u m p t i o n = \frac{\int_{0}^{t_{c y c l e}} \frac{V_{i n} P_{o u t} γ}{η (γ - 1)} [(P_{o u t} / P_{i n})^{1 - (1 / γ)} - 1] d t}{\int_{0}^{t_{c y c l e}} V_{p r o d u c t} y_{p r o d u c t} d t}$	(15)

表5 吸附剂参数

Table 5 Parameters of the adsorbent

参数	数值
S_BET/(m²·g^-1)	258
V_total/(cm³·g^-1)	0.357
V_mic/(cm³·g^-1)	4.77×10^-3
d/nm	4.73
ε_b	0.4
ε_p	0.73
r_p/m	3.26×10^-3
ρ_b/(kg·m^-3)	620
C_p_s/(kJ·kg^-1·K^-1)	850
HTC/(W·m^-2·K^-1)	235
k_g/(W·m^-1·K^-1)	0.024
k_s/(W·m^-2·K^-1)	0.2
$k_{L D F, H_{2}} / s^{- 1}$	0.01
$k_{L D F, N_{2}} / s^{- 1}$	0.005
$k_{L D F, N H_{3}} / s^{- 1}$	0.012
$D_{m, H_{2}} / (m^{2} \cdot s^{- 1})$	6.41×10^-5
$D_{m, N_{2}} / (m^{2} \cdot s^{- 1})$	2.13×10^-5
$D_{m, N H_{3}} / (m^{2} \cdot s^{- 1})$	2.13×10^-5
$C_{p g, H_{2}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	20.26
$C_{p g, N_{2}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	20.86
$C_{p g, N H_{3}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	11.39

表5 吸附剂参数

Table 5 Parameters of the adsorbent

参数	数值
S_BET/(m²·g^-1)	258
V_total/(cm³·g^-1)	0.357
V_mic/(cm³·g^-1)	4.77×10^-3
d/nm	4.73
ε_b	0.4
ε_p	0.73
r_p/m	3.26×10^-3
ρ_b/(kg·m^-3)	620
C_p_s/(kJ·kg^-1·K^-1)	850
HTC/(W·m^-2·K^-1)	235
k_g/(W·m^-1·K^-1)	0.024
k_s/(W·m^-2·K^-1)	0.2
$k_{L D F, H_{2}} / s^{- 1}$	0.01
$k_{L D F, N_{2}} / s^{- 1}$	0.005
$k_{L D F, N H_{3}} / s^{- 1}$	0.012
$D_{m, H_{2}} / (m^{2} \cdot s^{- 1})$	6.41×10^-5
$D_{m, N_{2}} / (m^{2} \cdot s^{- 1})$	2.13×10^-5
$D_{m, N H_{3}} / (m^{2} \cdot s^{- 1})$	2.13×10^-5
$C_{p g, H_{2}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	20.26
$C_{p g, N_{2}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	20.86
$C_{p g, N H_{3}} / (k J \cdot k g^{- 1} \cdot K^{- 1})$	11.39

表6 吸附塔参数

Table 6 Parameters of the adsorption column

参数	数值
H_b/m	0.44
D_b/m	0.0283
W_t/m	0.00175
ρ_w/(kg·m^-3)	7800
C_p_w/(kJ·kg^-1·K^-1)	0.502
h_w/(W·m^-2·K^-1)	60
h_amb/(W·m^-2·K^-1)	60
k_w/(W·m^-1·K^-1)	0.342

图3 NH3、N2和H2的平衡吸附量和吸附等温线

Fig.3 Equilibrium adsorption capacity and adsorption isotherms of NH3， N2 and H2

表7 NH3、N2和H2的吸附等温线拟合参数

Table 7 Fitting parameters of adsorption isotherms of NH3， N2 and H2

参数	NH₃	N₂	H₂
IP₁/(mmol·g^-1)	0.5315	7.442×10^-4	3.946×10^-4
IP₂/bar^-1	0.5675	0.5784	0.6080
IP₃	0.1653	1.011	0.9033
IP₄/K	517.2	1209	1074
IP₅/bar^-1	-0.06188	2.513×10^-3	-3.893×10^-4
IP₆/K	611.3	496.8	1461
R²	0.9905	0.9989	0.9959

表8 NH3、N2和H2的吸附热计算结果

Table 8 Calculation results of adsorption heat of NH3， N2 and H2

No.	H₂		N₂		NH₃
No.	q/(mmol·g^-1)	ΔH/(kJ·mol^-1)	q/(mmol·g^-1)	ΔH/(kJ·mol^-1)	q/(mmol·g^-1)	ΔH/(kJ·mol^-1)
1	0.001	9.90	0.004	9.96	0.331	26.41
2	0.005	9.97	0.018	10.01	0.905	26.96
3	0.008	10.03	0.032	10.06	1.479	27.39
4	0.012	10.10	0.047	10.12	2.053	27.73
5	0.016	10.16	0.061	10.17	2.627	28.00
6	0.020	10.22	0.076	10.23	3.201	28.23
7	0.024	10.28	0.090	10.29	3.775	28.43
8	0.028	10.34	0.105	10.35	4.350	28.60
9	0.032	10.39	0.119	10.41	4.924	28.74
10	0.036	10.44	0.134	10.47	5.498	28.87
11	0.040	10.49	0.148	10.53	6.072	28.98
12	0.043	10.54	0.163	10.60	6.646	29.08
Average		10.24		10.27		28.12

表9 工艺操作条件参数

Table 9 Parameters of the process operation

参数	数值
T_feed/K	298.15
T_amb/K	298.15
P_feed/bar	5.0
P_AD/bar	5.0
P_VU/bar	0.1
Q_feed/(mol·min^-1)	1.2
V_Buffer/m³	1.0×10^-3

表10 吸附床数学模型的初始条件

Table 10 Initial conditions for mathematical model of adsorption bed

初始条件
$y_{i} (z) = 0$ ， $y_{i n e r t} (z) = 1$ ， $q_{i} (z) = 0$ ， $q_{i n e r t} (z) = q_{i n e r t}^{*}$ ， $P (z) = P_{f e e d}$ ， $T_{g} (z) = T_{s} (z) = T_{w} (z) = T_{f e e d}$

表10 吸附床数学模型的初始条件

Table 10 Initial conditions for mathematical model of adsorption bed

初始条件
$y_{i} (z) = 0$ ， $y_{i n e r t} (z) = 1$ ， $q_{i} (z) = 0$ ， $q_{i n e r t} (z) = q_{i n e r t}^{*}$ ， $P (z) = P_{f e e d}$ ， $T_{g} (z) = T_{s} (z) = T_{w} (z) = T_{f e e d}$

表11 不同步骤下吸附床模型的边界条件

Table 11 Boundary conditions of adsorption bed models at different steps

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = 0} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = 0} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = 0} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Equalization depressurization（ED）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Co-current blowdown（CoD）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Vacuum（VU）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$P |_{z = 0} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$u_{0} |_{z = L} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Equalization repressurization（ER）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = L} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = L} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = L} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

Pressurization（PR）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = L} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = L} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = L} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

表11 不同步骤下吸附床模型的边界条件

Table 11 Boundary conditions of adsorption bed models at different steps

步骤

z=0

z=L

Adsorption（AD）

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = 0} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = 0} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = 0} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Equalization depressurization（ED）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Co-current blowdown（CoD）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$P |_{z = L} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Vacuum（VU）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$P |_{z = 0} = P_{o u t}$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

${\frac{\partial c_{i}}{\partial z}|}_{z = L} = 0$

$u_{0} |_{z = L} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = L} = 0$

Equalization repressurization（ER）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = L} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = L} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = L} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

Pressurization（PR）

${\frac{\partial c_{i}}{\partial z}|}_{z = 0} = 0$

$u_{0} |_{z = 0} = 0$

${\frac{\partial T_{g}}{\partial z}|}_{z = 0} = 0$

$\begin{matrix} u_{0, i n} c_{i n, i} |_{z = L} = u_{0} c_{i} - ε_{b} D_{a x} c \frac{\partial y_{i}}{\partial z} \end{matrix}$

$u_{0, i n} c_{i n} |_{z = L} = u_{0} c$

$u_{0, i n} c_{i n} C_{p} T_{i n} |_{z = L} = u_{0} c C_{p} T_{g} - k_{g} \frac{\partial T_{g}}{\partial z}$

表12 不同操作条件下模拟结果汇总

Table 12 Summary of simulation results under different operating conditions

序号	进料量/ (mol·min^-1)	原料气组成 (NH₃∶H₂∶N₂)/%（体积）	吸附时长/s	吸附压力/bar	纯度/%	回收率/%	能耗/(kJ·mol^-1)
1	1.2	15∶63.75∶21.25	230	5	88.78	95.28	37.78
2	1.2	15∶63.75∶21.25	240	5	89.04	94.99	37.90
3	1.2	15∶63.75∶21.25	250	5	89.30	94.67	38.02
4	1.2	15∶63.75∶21.25	260	5	89.54	94.32	38.19
5	1.2	15∶63.75∶21.25	270	5	89.77	93.94	38.35
6	0.8	15∶63.75∶21.25	250	5	85.29	99.72	35.80
7	1.0	15∶63.75∶21.25	250	5	87.75	98.38	38.34
9	1.4	15∶63.75∶21.25	250	5	90.42	88.48	40.57
10	1.6	15∶63.75∶21.25	250	5	91.06	81.59	43.92
11	1.2	15∶63.75∶21.25	250	4	89.58	87.90	35.48
12	1.2	15∶63.75∶21.25	250	4.5	89.51	91.83	36.73
13	1.2	15∶63.75∶21.25	250	5.5	89.03	96.55	39.45
14	1.2	15∶63.75∶21.25	250	6	88.51	98.10	40.75
15	1.2	10∶22.5∶67.5	250	5	84.45	98.74	46.48
17	1.2	12.5∶21.875∶65.625	250	5	87.23	97.09	44.66
18	1.2	17.5∶20.625∶61.875	250	5	91.00	91.20	33.75
19	1.2	20∶20∶60	250	5	92.23	87.23	33.67

图4 单塔VPSA压力曲线

Fig.4 Single-bed VPSA pressure profile

图5 吸附塔不同位置的温度分布

Fig.5 Temperature distribution at various positions of adsorption column

图6 不同步骤结束后NH3、N2和H2的固相浓度分布

Fig.6 Solid phase concentration distribution of NH3, N2, and H2 after different steps

图7 不同步骤结束后NH3、N2和H2的气相浓度分布

Fig.7 Gas phase concentration distribution of NH3, N2, and H2 after different steps

图8 吸附时长对纯度、回收率和能耗的影响

Fig.8 Effect of adsorption time on purity, recovery and energy consumption

图9 吸附压力对纯度、回收率和能耗的影响

Fig.9 Effect of adsorption pressure on purity, recovery and energy consumption

图10 进料量对纯度、回收率和能耗的影响

Fig.10 Effect of feed flowrate on purity, recovery and energy consumption

图11 原料气组成对纯度、回收率和能耗的影响

Fig.11 Effect of feed gas composition on purity, recovery and energy consumption

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