纯氧克劳斯工艺的模拟与优化

高德志; 喻昕蕾; 陶迅; 丁路; 代正华; 王辅臣

doi:10.14135/j.cnki.1006-3080.20201204003

纯氧克劳斯工艺的模拟与优化

doi: 10.14135/j.cnki.1006-3080.20201204003

华东理工大学上海市煤气化工程技术研究中心，上海 200237

基金项目: 国家自然科学基金(21978092)

详细信息

作者简介:
高德志(1996—)，男，福建泉州人，硕士生，研究方向为克劳斯工艺流程模拟与优化。E-mail：623686540@qq.com

通讯作者:
王辅臣，E-mail：wfch@ecust.edu.cn

中图分类号: TQ125.11
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-04
- 网络出版日期: 2021-01-25
- 刊出日期: 2022-02-23

Simulation and Optimization of Pure Oxygen Claus Process

Shanghai Engineering Research Center of Coal Gasification, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 基于Aspen Plus软件建立克劳斯工艺全流程模型，使用工厂数据进行验证，探究了进口酸气组成、氧气浓度及进气流量、氧气预热温度、炉膛压力及第二催化段反应器温度等工艺参数对克劳斯工艺的影响，并以Aspen Plus为优化工具，硫收率为目标函数计算了最佳操作参数。优化结果表明：总硫收率从优化前的98.31%提高到优化后的99.08%，尾气中主要污染物SO₂的排放量由优化前的0.350 kmol/h减少至优化后的0.278 kmol/h，降低了20.6%，并节省了酸性气体和空气预热所需的热量9133.38 J/mol。
- 克劳斯工艺 /
- 低浓度酸性气体 /
- 纯氧 /
- 流程模拟 /
- 优化
Abstract: The Claus process is effective for acid-gas processing and sulfur recovery. For industrial applications, combustion-supporting gas is needed to ensure flame stability when processing low-concentration acid gases, which can cause problems in terms of the increase in harmful substances such as polycyclic aromatic hydrocarbons and organic sulfur. The use of pure oxygen for combustion can not only increase the temperature in the furnace and improve the removal rate of hydrocarbon impurities, but also overcome the problems caused by the presence of combustion-supporting gas. In this paper, a full Claus-process model was constructed using the Aspen Plus software, and the theoretical result was validated by experimental data. The influences of the inlet acid gas composition, oxygen concentration, oxygen preheating temperature, furnace pressure, oxygen gas intake and the temperature of the second catalytic stage reactor on the Clause process were systematically examined. Optimized Aspen Plus was used to calculate the optimal operating parameters. The results showed that the sulfur recovery efficiency was enhanced from 98.31% to 99.08%, and the emission of SO₂, which was the main pollutant in the tail gas, was reduced from 0.350 kmol/h to 0.278 kmol/h; the reduction rate reached 20.6%. In addition, a heat of 9 133.38 J/mol (acid gas) was less consumed for the preheating of the acid gas and air.
- Claus process /
- low concentration acid gas /
- pure oxygen /
- process simulation /
- optimization

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图 1 Aspen Plus克劳斯硫回收工艺流程图

Figure 1. Schematic diagram of the Claus sulfur recovery process using Aspen Plus

AG—Acid gas；BG—Bypass gas；CD—Condenser；CR—Catalytic reactor；IR—Incinerator；PG—Process gas；PH—Preheater； RF—Reaction furnace；RS—Rstoic；SEP—Component separator；WHB—Waste heat boiler

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图 2 氧气摩尔分数对克劳斯硫回收过程的影响

Figure 2. Effect of oxygen molar fraction on the Claus sulfur recovery process

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图 3 氧气摩尔分数对n(H₂S)/n(SO₂)的影响

Figure 3. Effect of oxygen molar fraction on the n(H₂S)/n(SO₂)

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图 4 α对克劳斯硫回收过程的影响

Figure 4. Effect of α on the Claus sulfur recovery process

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图 5 α对总硫收率和第一催化段出口处n(H₂S)/n(SO₂)的影响

Figure 5. Effect of α on the total sulfur recovery efficiency and n(H₂S)/n(SO₂) of the first catalysis stage outlet

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图 6 氧气预热温度对克劳斯硫回收过程的影响

Figure 6. Effect of oxygen preheating temperature on the Claus sulfur recovery process

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图 7 炉膛压力对克劳斯过程总硫收率的影响

Figure 7. Effect of furnace pressure on the total sulfur recovery efficiency of the Claus process

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图 8 第二催化段反应器温度对克劳斯硫回收过程的影响

Figure 8. Effect of temperature of the second catalysis stage reactor on the Claus sulfur recovery process

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表 1 进料气组成及其参数

Table 1. Composition and parameters of the feed gas

Item	x/%										q/(kmol·h⁻¹)
Item	H₂	Ar	N₂	CO	CO₂	H₂S	H₂O	NH₃	O₂	CH₃OH	q/(kmol·h⁻¹)
AG1	0	0	29.00	0	20.00	50.00	0	0	0	1.00	49.107
AG2	0.50	0	20.00	0.50	67.00	2.00	0	0	0	10.00	8.036
AG3	12.40	0.20	0.20	8.00	75.00	1.00	3.00	0.20	0	0	15.625
Air1	0	0.93	78.09	0	0.03	0	0	0	20.95	0	60.902

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表 2 RF1内考虑的反应

Table 2. Considered reactions in RF1

No.	Reaction
1	$ {\rm{N}}{{\rm{H}}}_{3} \to {\rm{0.5N}}_{{2}}{+1.5}{{\rm{H}}}_{{2}} $
2	$ {{\rm{H}}_2}{\rm{S + 1}}{\rm{.5}}{{\rm{O}}_2} \to {{\rm{H}}_2}{\rm{O + S}}{{\rm{O}}_2}$

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表 3 RF2内的化学反应及其动力学参数

Table 3. Chemical reactions and kinetic parameters in RF2

No.	Reaction	Reaction rate expressions	Reference
3	${{\rm{H}}_{\rm{2}}}{{\rm{S}}} \leftrightarrow {{\rm{H}}_{\rm{2}}}{\rm{ + 0}}{\rm{.5}}{{\rm{S}}_{\rm{2}}}$	$-{r_{ {\rm{ {H} }_2S} } }=1.63\times{10^{-1} }{ {\rm{e} }^{{\frac{ {45.1} }{ {RT} } } } }{p_{_ { {\rm{H} }_{2}{\rm{S} } } } }p_{\rm{S_2} }^{0.5}-1.36\times{10^{-6} }{ {\rm{e} }^{{\frac{ {23.4} }{ {RT} } } } }{p_{_{\rm{H_2} }} }{p_{_{\rm{S_2}} } }$	[19]
4	${\rm{CO} } + 0.5{{\rm{S}}_2} \leftrightarrow {\rm{COS}}$	$- {r_{ {\rm{CO} } } } = 3.18\times {10^5}{ {\rm{e} }^{{\frac{ {15.3} }{ {RT } } } }}\left( { {c_{\rm{CO} } }{c_{ { {\rm{S} }_2} } } - \dfrac{1}{ { {k_{\rm{eq2} } } } }{c_{\rm{COS} } }c_{ { {\rm{S} }_2} }^{0.5} } \right)$	[20]
5	$ {\rm{C}}{{\rm{O}}_{\rm{2}}}{\rm{ + }}{{\rm{H}}_{\rm{2}}} \leftrightarrow {\rm{CO + }}{{\rm{H}}_{\rm{2}}}{\rm{O}}$	$-{r_{\rm{C{O_2} } } }=8.59\times{10^{10} }{ {\rm{e} }^{{\frac{ {64.7} }{ {RT} } } } }\left( { {c_{\rm{C{O_2} } } }c_{ {\rm{ {H} }_2} }^{0.5}-\dfrac{1}{ { {k_{{\rm{eq}}3} } } }\dfrac{ { {c_{\rm{CO} } }{c_{ {\rm{ {H} }_2O} } } } }{ {c_{ {\rm{ {H} }_2} }^{0.5} } } } \right)$	[21]
6	$ {\rm{CO + }}{{\rm{H}}_{\rm{2}}}{\rm{S}} \leftrightarrow {\rm{COS + }}{{\rm{H}}_{\rm{2}}} $	$-r{\rm{_{CO} } }=1.59\times{10^5}{ {\rm{e} }^{{\frac{ {26.5} }{ {RT} } } } }\left({ {c_{\rm{CO} } }c_{ {\rm{ {H} }_2S} }^{0.5}-\dfrac{1}{ { {k_{{\rm{eq}}4} } } }\dfrac{ { {c_{\rm{COS} } }{c_{ {\rm{ {H} }_2} } } } }{ {c_{ {\rm{ {H} }_2S} }^{0.5} } } }\right)$	[22]
7	$ {{\rm{H}}_{\rm{2}}}{\rm{S + 0}}{\rm{.5S}}{{\rm{O}}_{\rm{2}}} \leftrightarrow {\rm{0}}{\rm{.75}}{{\rm{S}}_{\rm{2}}}{\rm{ + }}{{\rm{H}}_{\rm{2}}}{\rm{O}}$	$-{r_{ {\rm{ {H} }_2S} } } =3.18\times{10^3}{ {\rm{e} }^{{\frac{ {14.3} }{ {RT} } } } }{c_{ {\rm{ {H} }_2S} } }c_{\rm{S{O_2} } }^{0.5}-3.11\times{10^1}{ {\rm{e} }^{{\frac{ {8.5} }{ { {RT} } } }} }{c_{\rm{ { { {H} }_2}O} } }c_{ {\rm{S_2} } }^{0.75}$	[23]

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表 4 炉膛出口气流量模拟结果与工厂数据比较

Table 4. Simulated results versus plant data for flow rate of gas from furnace

Gas	q/(kmol·h⁻¹)		Absolute error/%
Gas	Plant date	Simulated results	Absolute error/%
H₂	1.636	1.698	3.81
Ar	0.600	0.600	0.01
N₂	63.453	63.448	0.01
CO	1.038	1.233	18.77
CO₂	27.079	26.868	0.78
H₂S	9.155	9.175	0.22
COS	0.119	0.133	12.13
SO₂	4.637	4.789	3.27
H₂O	17.930	17.836	0.53
S₂	5.458	5.387	1.31

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表 5 重要参数优化前后结果比较

Table 5. Important parameters contrast of the optimization results

Item	x(O₂)/%	Split ratio	q_Air/(kmol·h⁻¹)	T₀/℃	T_a/℃	T_S/℃	T_f/℃	Y_S/%	n(H₂S)/n(SO₂) of the first catalysis stage	${q}_{_{\rm{{SO_{2}}}, {\rm{outlet}}}}$/ (kmol·h⁻¹)
Before optimization	20.95	0.80	60.90	80	240	218	1019.39	98.31	1.99	0.350
After optimization	99.60	1.00	14.09	25	25	180	1314.11	99.08	2.00	0.278

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