双膜耦合分离器的研究及应用
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摘要
在中空纤维膜分离器内进行气体分离时,慢气在原料侧的富集降低了快气的传质推动力,对快气的渗透产生不利影响。提出使用双膜耦合分离器来减弱此影响,进而提高膜过程的分离效率。建立了描述双膜耦合分离器在全混流,并流,逆流三种流型下分离混合气体的数学模型,并把求解过程嵌入到UniSim软件中进行求解,和文献中实验值相比较,逆流模型计算值吻合最好。
以回收煤气化过程中一氧化碳变换气里所含的H：为背景,通过计算分析了各参数对双膜耦合分离器性能的影响。结果表明,逆流比并流更有利于气体的分离；适当增大两膜的膜面积比有利于H2的回收,同时也证明双膜耦合分离器的性能优于单膜分离器；增大原料气的进料压力可以提高H2在PEI膜渗透侧的浓度和回收率,有利于H2的回收；提高双膜耦合分离器中两种膜的性能(增大渗透速率和分离系数)可以显著提高膜分离器的分离性能。比较了两单膜分离器串联和双膜耦合分离器分离混合气体的性能,结果表明当膜面积比为0.6时,对于H2的回收,双膜耦合分离器可以得到最高的回收率,但PEO-PEI串联可以得到最高的氢气浓度。
针对国内某大型综合炼油化工企业内的多股炼厂尾气,开发出了炼厂尾气综合回收工艺来回收其中的氢气和轻烃等组分。该工艺分为氢气回收、轻烃回收和双膜耦合分离三个部分,相关技术主要包括压缩冷凝、气体脱硫、变温吸附脱水、氢膜分离、有机蒸汽膜分离、精馏等。年可回收氢气6.1×107Nm3、液化石油气13.1万吨、轻油1万吨,工艺中分离出的各股物料的质量满足该炼厂将其作为产品或生产原料的要求,通过初步的经济性分析该工艺年经济效益可达2.8×108元。
把双膜耥合分离器用于压缩冷凝不凝气的回收,和多级膜串联方案相比,轻烃的回收率由82.8%t增大到98.7%,对于20万吨/年炼厂气的回收,年经济收益可增加919万元。使用三种方案回收PSA解吸气中的氢气,双膜耦合分离器方案和单PEI膜方案相比,PEI膜渗透气中氢气浓度由74.38%增加到80.12%,氢气回收率由48.24%增加到54.66%,但PEO-PEI串联方案可以得到最高的氢气浓度和回收率,分别为83.46%和56.18%。
In the hollow fiber membrane separator for gas separation, the enrichment of slow gas in the feed side reduced mass transfer impetus of fast gas, which had an adverse effect on the permeability of fast gas. It was proposed that using double membrane coupling separator to reduce this effect, and to improve the separation efficiency of the membrane process.The mathematical model was established to express gas separation process in double membrane coupling separator with three flow patterns, which were perfect mixing, cocurrent and countercurrent. The solving procedure was embedded into the UniSim software for solving. Compared the model calculation values with the experimental values in the literature, countercurrent flow pattern was preferable.
Choose the recovery of H2from carbon monoxide shift gas in coal gasification as background, the influence of various parameters on the performance of double membrane coupling separator was analysised.The results show that:countercurrent is more advantageous to the gas separation than the cocurrent flow pattern; increasing the membrane area ratio is in favor of H2recovery, and the performance of double membrane coupling separator is better than the single membrane separator; increasing the feed pressure can increase the H2concentration and recovery rate in the permeate side of the PEI membrane; improving the performance of two kinds of membranes in double membrane coupling separator (increase the permeation rate and separation coefficient) can improve the membrane separation performance. The performance of two single membrane separator in series scheme was compared with the double membrane coupling separator for separating mixed gas.the results showed that for recovery of H2, double membrane coupling separator can get the highest recovery rate, but the PEO-PEI series can get the highest molar content.
A comprehensive recovery process was developed to recover hydrogen and light hydrocarbon from refinery vent gases in a large petrochemical plant. The process composed of three parts:hydrogen recovery, light hydrocarbon recovery and multistage membrane separation. The technology used in the process included compression/condensation, gas desulfurization, TSA dehydration, hydrogen membrane separation, VOC membrane separation and distillation. The annual production of H2, LPG, and light petroleum are6.1×107Nm3,1.31×105ton, and1×104ton respectively. The quality of the materials separated through the process meets the requirement that they can be used as products or production materials by the plant. Through the primary economic analysis, the annual economic benefit of the process reached2.8×108yuan.
Double membrane coupling separator was used for uncondensed gas recovery, the light hydrocarbon recovery rate increased from82.8%to98.7%compared with multistage membrane separation, for the200000tons/year refinery gases recovery, the annual economic benefits increased9.19million yuan. Three schemes was used to recover H2from PSA purge gas, compared the PEI membrane separator scheme with the double membrane coupling separator scheme, the H2concentration increased from74.38%to80.12%, H2recovery rate from48.24%to54.66%, but the PEO-PEI series scheme get the highest H2concentration and recovery rate of83.46%and56.18%respectively.
以回收煤气化过程中一氧化碳变换气里所含的H：为背景,通过计算分析了各参数对双膜耦合分离器性能的影响。结果表明,逆流比并流更有利于气体的分离；适当增大两膜的膜面积比有利于H2的回收,同时也证明双膜耦合分离器的性能优于单膜分离器；增大原料气的进料压力可以提高H2在PEI膜渗透侧的浓度和回收率,有利于H2的回收；提高双膜耦合分离器中两种膜的性能(增大渗透速率和分离系数)可以显著提高膜分离器的分离性能。比较了两单膜分离器串联和双膜耦合分离器分离混合气体的性能,结果表明当膜面积比为0.6时,对于H2的回收,双膜耦合分离器可以得到最高的回收率,但PEO-PEI串联可以得到最高的氢气浓度。
针对国内某大型综合炼油化工企业内的多股炼厂尾气,开发出了炼厂尾气综合回收工艺来回收其中的氢气和轻烃等组分。该工艺分为氢气回收、轻烃回收和双膜耦合分离三个部分,相关技术主要包括压缩冷凝、气体脱硫、变温吸附脱水、氢膜分离、有机蒸汽膜分离、精馏等。年可回收氢气6.1×107Nm3、液化石油气13.1万吨、轻油1万吨,工艺中分离出的各股物料的质量满足该炼厂将其作为产品或生产原料的要求,通过初步的经济性分析该工艺年经济效益可达2.8×108元。
把双膜耥合分离器用于压缩冷凝不凝气的回收,和多级膜串联方案相比,轻烃的回收率由82.8%t增大到98.7%,对于20万吨/年炼厂气的回收,年经济收益可增加919万元。使用三种方案回收PSA解吸气中的氢气,双膜耦合分离器方案和单PEI膜方案相比,PEI膜渗透气中氢气浓度由74.38%增加到80.12%,氢气回收率由48.24%增加到54.66%,但PEO-PEI串联方案可以得到最高的氢气浓度和回收率,分别为83.46%和56.18%。
In the hollow fiber membrane separator for gas separation, the enrichment of slow gas in the feed side reduced mass transfer impetus of fast gas, which had an adverse effect on the permeability of fast gas. It was proposed that using double membrane coupling separator to reduce this effect, and to improve the separation efficiency of the membrane process.The mathematical model was established to express gas separation process in double membrane coupling separator with three flow patterns, which were perfect mixing, cocurrent and countercurrent. The solving procedure was embedded into the UniSim software for solving. Compared the model calculation values with the experimental values in the literature, countercurrent flow pattern was preferable.
Choose the recovery of H2from carbon monoxide shift gas in coal gasification as background, the influence of various parameters on the performance of double membrane coupling separator was analysised.The results show that:countercurrent is more advantageous to the gas separation than the cocurrent flow pattern; increasing the membrane area ratio is in favor of H2recovery, and the performance of double membrane coupling separator is better than the single membrane separator; increasing the feed pressure can increase the H2concentration and recovery rate in the permeate side of the PEI membrane; improving the performance of two kinds of membranes in double membrane coupling separator (increase the permeation rate and separation coefficient) can improve the membrane separation performance. The performance of two single membrane separator in series scheme was compared with the double membrane coupling separator for separating mixed gas.the results showed that for recovery of H2, double membrane coupling separator can get the highest recovery rate, but the PEO-PEI series can get the highest molar content.
A comprehensive recovery process was developed to recover hydrogen and light hydrocarbon from refinery vent gases in a large petrochemical plant. The process composed of three parts:hydrogen recovery, light hydrocarbon recovery and multistage membrane separation. The technology used in the process included compression/condensation, gas desulfurization, TSA dehydration, hydrogen membrane separation, VOC membrane separation and distillation. The annual production of H2, LPG, and light petroleum are6.1×107Nm3,1.31×105ton, and1×104ton respectively. The quality of the materials separated through the process meets the requirement that they can be used as products or production materials by the plant. Through the primary economic analysis, the annual economic benefit of the process reached2.8×108yuan.
Double membrane coupling separator was used for uncondensed gas recovery, the light hydrocarbon recovery rate increased from82.8%to98.7%compared with multistage membrane separation, for the200000tons/year refinery gases recovery, the annual economic benefits increased9.19million yuan. Three schemes was used to recover H2from PSA purge gas, compared the PEI membrane separator scheme with the double membrane coupling separator scheme, the H2concentration increased from74.38%to80.12%, H2recovery rate from48.24%to54.66%, but the PEO-PEI series scheme get the highest H2concentration and recovery rate of83.46%and56.18%respectively.
引文
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[2]STERN S A. Polymers for gas separations:the next decade[J]. Journal of Membrane Science,1994,94(1):1-65.
[3]WIJMANS J G, BAKER R W. The solution-diffusion model:a review[J]. Journal of Membrane Science,1995,107(1-2):1-21.
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