回收费托合成弛放气中合成原料的研究
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摘要
我国石油对外依存度逐年增大,而石油进口来源高度集中、运输方式单一和国际油价波动剧烈等问题严重威胁了我国的石油安全,迫使我国建立石油战略安全体系。建立以煤炭、天然气和煤层气等为原料生产的合成气,通过费托合成工艺制合成油的技术储备,可以有效地保证我国石油战略资源安全。合成气经过费托合成工艺制备合成油的过程中,由于原料合成气中N_2、Ar等惰性气体在合成过程中不断积累,浓度会逐渐升高,造成反应物分压的降低,从而降低了原料转化率。因此为控制反应装置中惰性气体的含量,系统必须定期排出一定量的弛放气。但弛放气中含有大量合成原料,如果直接排入燃料管网会降低其价值;并且因为弛放气中不含毒害催化剂的组分,所以从弛放气中回收的H_2和CO直接返回合成装置,可以大大降低合成产品的单耗、提高过程的经济效益和产品竞争力。
本文以费托合成弛放气为回收目标,针对弛放气的组成和压力等特点提出了先用膜分离工艺回收氢气,后用PSA工艺回收CO的综合回收过程。模拟了两种氢气分离膜组件的氢气回收过程,讨论了产品氢气浓度和渗透侧压力对回收效果和经济效益的影响,确定了氢气回收过程的操作条件:选用PI制备的膜组件,一段回收过程,渗透侧表压为100kPa。确定PSA进气压力为0.8MPag,采用5-1-1/RP VPSA回收流程。综合回收过程的H_2回收率为89.0%,CO回收率为83.4%,经济效益为3.77亿元/年,投资回收期15个月。
针对弛放气回收过程有两个目标回收组分和排出系统物流组成的特点对回收过程进行优化,首先比较了CO吹扫膜组件和H_2吹扫PSA两种回收流程的经济效益,确定H_2吹扫PSA为较优流程。在此基础上,讨论了PSA吸附尾气回收和PSA置换尾气回收流程。结果表明:在现有的燃料气和合成气价格条件下,置换尾气回收过程有较高的经济效益。讨论了系统的处理量和稳定性,得到系统最大处理量为设计处理量的120%:并得到不同αH_2/N_2时,更换膜组件的临界点。
目前使用的膜组件计算模型忽略了膜丝内压降,而实际膜分离过程中膜丝内压降经常是不可忽略的,本文改进了HYSYS中的Membrane Extension模块,采用更接近实际的柱塞流模型代替原有的全混流模型,计算过程增加了膜丝内径、丝外径和膜长度等变量,并把其引入Unisim Design中。采用改进的计算模块与原有的模块相比,可得到更接近实际的计算结果。
National energy safety is seriously threatened by increasing degree of dependence on foreign petrol,highly centralized imported sources of oil,single transportation mode and acute fluctuation of the international oil's price,which force our country to construct petrol security strategy system.To establish the technical reserve of synthesis oil technology by F-T synthesis could effectively ensure national petrol strategic security.The Inert gas such as N_2, Ar,CH_4 et al could accumulate during synthesis process.So the concentration of the inert gas increases gradually,which could decrease the partial pressure of reactants,affect the balance of the F-T synthesis reaction,and reduce the conversion rate of raw materials.Synthesis system must exhaust a certain amount of vent gas in order to control the concentration of the inert gas.The vent gas usually as fuel gas imports the fuel pipe network,which decrease the value of vent gas.H_2 and CO recovered from vent gas could directly return to the synthesis device due to the vent gas doesn't contain catalyst poison gas,so recovery H_2 and CO from vent gas could effectively reduce the unit consumption of synthesis product,increase the economic benefit of recovery process and product competition.
According to the characteristics of vent gas's pressure and composition,this paper proposed the integrated recovery process composed of membrane separation and PSA. Unisim Design software is utilized to simulate the recovery process of membrane modules prepared by PSf and PI.The effects of product hydrogen concentration and pressure in the permeate on hydrogen recovery rate and economic benefit have been discussed.The initial condition of hydrogen recovery is choosing membrane module made from PI with one-stage recovery process,and 100kPag as the pressure in the permeate.The entrance pressure of PSA is determined according to the pressure of fuel pipe network and CO as the adsorbed gas,and the PSA-CO recovery process adopts 5-1-1/RP VPSA technique.In the whole process,the recoveries of H_2 and CO are 89.0%and 83.4%respectively,the economic benefit is 3.77 billion yuan per year and the investment payback period is 15 months.
The integrated recovery process has been optimized according to the recovery process characteristics and components of material flow exhausted from process.First,the process economic benefits of the CO purging membrane module and H_2 purging PSA have been compared and the process of H_2 purging PSA is the better scheme.The processes of adsorption tail gas recovery and replacement gas recovery have been discussed on above basis. The results show that replacement gas recovery process has higher economic benefit,about 3.87 billion yuan per year in present prices of synthesis gas and fuel gas,the recoveries of H_2 and CO are 89.0%and 93.5%respectively and the investment payback period is 15 months. The maximum capacity and stability of recovery process have been discussed,the results show that the maximum capacity is 1.2 times as much as the designed capacity.In the condition of present prices of membrane modules and synthesis gas,whenαH_2/N_2 is less than 95,the economic benefit of membrane modules replacement is higher.The product hydrogen concentration is greatly affected by CO_2 concentration of vent gas,but the effect ofαCO_2/N_2 on hydrogen recovery process can be neglected.
The pressure drop in hollow-fiber membrane is necessary factor in actual application. Membrane Extension module of Unisim Design has been improved because the pressure drop in hollow-fiber membrane was neglected in the initial module.Improved module adds parameters such as inner diameter,external diameter and length of hollow-fiber membrane. Module adopts differential calculation equations and four-order Runge-Kutta method. Improved module compared with initial module could obtain calculation results that are more close to experimental values.
本文以费托合成弛放气为回收目标,针对弛放气的组成和压力等特点提出了先用膜分离工艺回收氢气,后用PSA工艺回收CO的综合回收过程。模拟了两种氢气分离膜组件的氢气回收过程,讨论了产品氢气浓度和渗透侧压力对回收效果和经济效益的影响,确定了氢气回收过程的操作条件:选用PI制备的膜组件,一段回收过程,渗透侧表压为100kPa。确定PSA进气压力为0.8MPag,采用5-1-1/RP VPSA回收流程。综合回收过程的H_2回收率为89.0%,CO回收率为83.4%,经济效益为3.77亿元/年,投资回收期15个月。
针对弛放气回收过程有两个目标回收组分和排出系统物流组成的特点对回收过程进行优化,首先比较了CO吹扫膜组件和H_2吹扫PSA两种回收流程的经济效益,确定H_2吹扫PSA为较优流程。在此基础上,讨论了PSA吸附尾气回收和PSA置换尾气回收流程。结果表明:在现有的燃料气和合成气价格条件下,置换尾气回收过程有较高的经济效益。讨论了系统的处理量和稳定性,得到系统最大处理量为设计处理量的120%:并得到不同αH_2/N_2时,更换膜组件的临界点。
目前使用的膜组件计算模型忽略了膜丝内压降,而实际膜分离过程中膜丝内压降经常是不可忽略的,本文改进了HYSYS中的Membrane Extension模块,采用更接近实际的柱塞流模型代替原有的全混流模型,计算过程增加了膜丝内径、丝外径和膜长度等变量,并把其引入Unisim Design中。采用改进的计算模块与原有的模块相比,可得到更接近实际的计算结果。
National energy safety is seriously threatened by increasing degree of dependence on foreign petrol,highly centralized imported sources of oil,single transportation mode and acute fluctuation of the international oil's price,which force our country to construct petrol security strategy system.To establish the technical reserve of synthesis oil technology by F-T synthesis could effectively ensure national petrol strategic security.The Inert gas such as N_2, Ar,CH_4 et al could accumulate during synthesis process.So the concentration of the inert gas increases gradually,which could decrease the partial pressure of reactants,affect the balance of the F-T synthesis reaction,and reduce the conversion rate of raw materials.Synthesis system must exhaust a certain amount of vent gas in order to control the concentration of the inert gas.The vent gas usually as fuel gas imports the fuel pipe network,which decrease the value of vent gas.H_2 and CO recovered from vent gas could directly return to the synthesis device due to the vent gas doesn't contain catalyst poison gas,so recovery H_2 and CO from vent gas could effectively reduce the unit consumption of synthesis product,increase the economic benefit of recovery process and product competition.
According to the characteristics of vent gas's pressure and composition,this paper proposed the integrated recovery process composed of membrane separation and PSA. Unisim Design software is utilized to simulate the recovery process of membrane modules prepared by PSf and PI.The effects of product hydrogen concentration and pressure in the permeate on hydrogen recovery rate and economic benefit have been discussed.The initial condition of hydrogen recovery is choosing membrane module made from PI with one-stage recovery process,and 100kPag as the pressure in the permeate.The entrance pressure of PSA is determined according to the pressure of fuel pipe network and CO as the adsorbed gas,and the PSA-CO recovery process adopts 5-1-1/RP VPSA technique.In the whole process,the recoveries of H_2 and CO are 89.0%and 83.4%respectively,the economic benefit is 3.77 billion yuan per year and the investment payback period is 15 months.
The integrated recovery process has been optimized according to the recovery process characteristics and components of material flow exhausted from process.First,the process economic benefits of the CO purging membrane module and H_2 purging PSA have been compared and the process of H_2 purging PSA is the better scheme.The processes of adsorption tail gas recovery and replacement gas recovery have been discussed on above basis. The results show that replacement gas recovery process has higher economic benefit,about 3.87 billion yuan per year in present prices of synthesis gas and fuel gas,the recoveries of H_2 and CO are 89.0%and 93.5%respectively and the investment payback period is 15 months. The maximum capacity and stability of recovery process have been discussed,the results show that the maximum capacity is 1.2 times as much as the designed capacity.In the condition of present prices of membrane modules and synthesis gas,whenαH_2/N_2 is less than 95,the economic benefit of membrane modules replacement is higher.The product hydrogen concentration is greatly affected by CO_2 concentration of vent gas,but the effect ofαCO_2/N_2 on hydrogen recovery process can be neglected.
The pressure drop in hollow-fiber membrane is necessary factor in actual application. Membrane Extension module of Unisim Design has been improved because the pressure drop in hollow-fiber membrane was neglected in the initial module.Improved module adds parameters such as inner diameter,external diameter and length of hollow-fiber membrane. Module adopts differential calculation equations and four-order Runge-Kutta method. Improved module compared with initial module could obtain calculation results that are more close to experimental values.
引文
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