MDEA-TBEE复合溶液选择性吸收H_2S性能评价

将一种强空间位阻胺TBEE(叔丁氨基乙氧基乙醇)添加于MDEA(N-甲基二乙醇胺)溶液中形成复合溶液MDEA-TBEE,以填料柱为反应器,采用常压吸收-常压再生操作流程,研究了复合溶液从混合气中选择性吸收H2S吸收性能,并与单组分吸收剂MDEA溶液吸收性能作比较,以脱除率、选择性、溶液负载和容量为评价指标,评价了再生温度、原料气CO2/H2S摩尔比、气液比和贫液负载等因素对复合溶液选择性吸收H2S性能的影响。结果表明,复合溶液比MDEA溶液易于再生,H2S脱除率高于MDEA溶液;复合溶液的容量大于MDEA溶液,平均是MDEA的1.25倍;随着气液比增大,H2S脱除率下降,选择性有所上升。     

浅谈聚乙二醇二甲醚与醇胺的复配

聚乙二醇二甲醚是酸性气体的物理吸收剂,醇胺是酸性气体的化学吸收剂,二者的复配是优良的脱硫、脱碳溶剂.介绍了聚乙二醇二甲醚与二异丙醇胺(DIPA)、三乙二醇单甲醚与甲基二乙醇胺(MDEA)混合复配方法;论述了复合溶剂的吸收能力、反应热、最合适溶液成分配比和适宜的工艺技术;以天然气和氨气混合气为例,介绍了醚胺法气体净化的工艺过程和应用效果.     

一步法催化氧化COS脱硫技术

近日，由南化集团研究院承担的江苏省科研院所专项资金项目“位阻胺脱硫脱碳系列溶剂的研究开发”通过了江苏省科技厅组织的科技成果验收。该院开发了以位阻胺为主体的脱硫脱碳系列复合胺溶剂，并建成500t／a系列溶剂的中试生产装置。该溶剂与MDEA溶液相比，吸收硫化物的负荷提高100％以上；在处理气量提高40%的条件下，净化气中总硫降低50％以上；位阻胺回收低分压CO2溶剂和位阻胺(NCMA)溶剂与其它胺法脱碳溶剂相比，具有吸收速度快、能力大、净化度高和能耗低等优点。项目申报了7项国家专利，并有2项获得授权，位阻胺脱硫溶剂填补了国内空白，项目的总体技术达到了国际先进水平。     

有机醇胺溶液中H2S气体溶解性能评价

以H2S和N2的混合气为模拟天然气,采用自制的小型的气液吸收平衡装置,考察了吸收剂、吸收剂浓度、温度对有机醇胺溶液吸收性能的影响。采用Aspen Hysys和Aspen Plus两大化工工艺流程模拟软件进行模拟计算,发现实验结果与模拟计算结果相吻合。以N-甲基二乙醇胺（MDEA）作萃取剂,吸收剂浓度为2.5 mol/L,吸收剂温度为25 ℃时,吸收剂的吸收负荷为3183.5 mg/L。     

DETA-MDEA复合溶液吸收与解吸CO2实验研究

以烯胺吸收剂DETA(二乙烯三胺)为主吸收剂与辅助吸收剂MDEA(N-甲基二乙醇胺)按摩尔配比20:1～20:6进行复配,通过一次循环吸收、解吸实验,对比其在313 K温度下的吸收量、吸收速率以及393 K温度下的再生速率、再生量以及它们的降解率。以筛选出较好的20:4DETA+MDEA烯胺复配药剂为基础,进行6次循环吸收-解吸实验,考察循环吸收、解吸性能与胺降解率;以智能高压反应釜分别考察了20:4DETA+MDEA降解性能,对CO_2负载、温度、铁离子的降解性能的影响进行了探讨。     

新型相变有机胺吸收捕集CO2技术研究进展

CO₂捕集、利用与封存(CCUS)技术是实现碳减排的关键技术之一,有机胺吸收技术是目前研究最广泛、最成熟的CO₂捕集技术,已有少数工业应用案例。吸收剂是吸收技术的核心,吸收剂的研发创新是该领域的热点方向。相比于单一相的有机胺吸收剂,相变吸收剂在吸收CO₂后产生相变行为,仅需对富相进行再生,可大幅减少再生体积,降低再生能耗。本文介绍了传统混合胺相变吸收体系的典型工艺、吸收机理和吸收剂研究进展,分析了吸收剂吸收CO₂后富相黏度高、富相体积占比大及其导致的再生能耗增加的问题。本文系统梳理了为解决上述问题而研发的四种新型的相变吸收体系,分别为空间位阻胺混合型相变吸收剂、物理溶剂混合型相变吸收剂、醇胺混合型相变吸收剂、催化剂-有机胺复合型相变吸收剂,对各类新型相变吸收体系的设计构建原理及性能强化机制进行了分析。最后,基于对研究进展的深入分析,提出了相变吸收剂的未来研究方向。     

AMP吸收电厂烟气CO_2性能的实验

电厂烟气CO2捕集目前以醇胺法中的MEA为主,但MEA吸收剂的CO2吸收总量较低,对设备有腐蚀性。空间位阻胺作为一种新兴的吸收剂,具有较快的吸收速率和较大的吸收量,在烟气脱碳方面越来越引起重视。本文设计了一套小试实验装置,测试了不同浓度的MEA和AMP吸收烟气CO2的实验,对比了其吸收速率和总吸收量,分析了AMP溶液吸的收速率随溶液pH值和吸收剂浓度的变化规律,为空间位阻胺在电厂烟气脱碳工业中的应用提供理论指导。     

MDEA活化胺液在天然气预处理工艺中的吸收性能

目前天然气预处理工业中存在各种不同类型的胺液活化剂,不同的胺液活化剂具有各自的优缺点,其中,最常用的是甲基二乙醇胺(MDEA)的活化胺液。本文通过实验研究了以MDEA为主吸收剂,添加5种不同种类胺液活化剂(MEA、DEA、TEA、DETA、TETA)的吸收性能,包括吸收速率、吸收负荷等,并对实验结果进行了对比分析。实验结果表明:在本文实验条件下,MDEA与伯胺、仲胺的混合胺液吸收负荷较高,综合脱碳效果较好;MDEA与烯胺的混合胺液可以显著提高反应速率,但会受到胺液中CO2负荷的影响;TEA吸收速率最慢,不适合做MDEA的活化剂。本文研究内容为混合胺液工业应用提供了技术指导。     

基于分子管理的脱有机硫复配型溶剂的开发与应用

基于分子管理理念, 对脱有机硫复配型溶剂进行组成设计。采用两维溶解度参数理论, 筛选出与甲硫醇溶解度参数接近的溶剂作为复配溶剂中提高甲硫醇脱除率的组分;并根据胺的碱性、空间位阻效应对其与COS反应速率的影响规律, 选择具有较小空间位阻效应和适当强度碱性的环状胺类作为提高COS脱除率的溶剂组分。根据原料气的有机硫分布特点, 将所筛选的溶剂组分按一定比例配入N-甲基二乙醇胺(MDEA)中, 获得了两种复配溶剂(UDS-I, UDS-II)。脱硫实验结果表明, 对于COS占有机硫总量94%的天然气, UDS-I溶剂的COS脱除率较MDEA高出近44个百分点, 其净化天然气质量满足一类气的指标要求;对于甲硫醇占有机硫总量79%的焦化液化气, UDS-II溶剂的甲硫醇脱除率较MDEA高出近50个百分点, 其净化液化气的总硫含量满足民用液化气指标要求。     

填料塔中混合胺吸收二氧化碳的研究

在填料塔中考察了常压下混合胺吸收剂[20%乙醇胺(MEA)+2% N-甲基二乙醇胺(MDEA),20%羟乙基乙二胺(AEE)+2% MDEA]对CO_2的吸收与解吸效果.同时测得了AEE+MDEA混合胺体系吸收剂脱除空气中体积分数约10%的CO_2的体积总传质系数K_Ga_v的近似值,并考察了进口气体中CO_2摩尔流量、气体流量、液体流量等因素对K_Ga_v的影响.实验结果表明,AEE+MDEA吸收效果明显好于MEA+MDEA,并且二者解吸效果相同;K_Ga_v随CO_2摩尔流量、气体流量、液体流量增大而增大.     

CO2 Absorption into Aqueous Solutions of a Polyamine (PZEA), a Sterically Hindered Amine (AMP), and their Blends

Among numerous techniques existing for reducing CO₂ emissions, CO₂ capture by absorption in aqueous alkanolamine solutions was specifically studied in this work. For the choice of the adequate amine solution, two major criteria must be taken into account: absorption performances (higher with primary and secondary amines) and energy costs for solvent regeneration (more interesting with tertiary and sterically hindered amines). The different types of amines can also be mixed in order to combine the specific advantages of each type of amines, an activation phenomenon being observed. Aqueous solutions of (piperazinyl‐1)‐2‐ethylamine (PZEA, a polyamine known as absorption activator) and 1‐amino‐2‐propanol (AMP, a sterically hindered amine), pure or mixed with other amines, are experimentally compared with respect to CO₂ removal performances by means of absorption test runs achieved in a special gas‐liquid contactor at 25 °C. The positive impact of addition of PZEA to monoethanolamine (MEA), N‐methyldiethanolamine (MDEA), and AMP solutions was clearly highlighted. The absorption performances have also been satisfactorily simulated with coherent physicochemical data.     

Non-oxidative thermal degradation of amines: GCMS/FTIR spectra analysis and molecular modeling

Aqueous amino solvents, such as monoethanolamine (ETA/MEA), methyl diethanolamine (MDEA) or amine blends, are the most widely used solvents in commercial CO₂ or acid gas separation applications. These commercial solvents have various disadvantages, such as the possibilities of the solvent to be degraded. This research examines the impact of non-oxidative thermal degradations on the performance of the CO₂ absorption and the degradation mechanism of amine solvents. The impact of degradation was conducted by measuring the CO₂ solubility of solvent that had been heated to 120°C for 2 h. Although the performance of CO₂ absorption was not significantly reduced, the degradation of amines was found. Supported by Fourier Transform Infrared (FTIR) and Gas Chromatography/Mass Spectrometer result, the suspected products of non-oxidative thermal degradation of MDEA were MEA and acetone.     

Comprehensive evaluation and sensitivity analysis of regeneration energy for acid gas removal plant using single and activated-methyl diethanolamine solvents

The absorption of acid gas using reactive amines is among the most widely used types of capturing technologies. However, the absorption process requires intensive energy expenditure majorly in the solvent regeneration process. This study simultaneously evaluated the regeneration energy of MDEA and PZ/MDEA solvents in terms of heat of absorption, sensible heat, and vaporization heat. Aspen Hysys version 8.8 simulation tool is applied to model the full acid gas removal plant for the chemical absorption process. The new energy balance technique presents around the absorption and desorption columns to bring a new perspective of energy distribution in the capturing of acid gas plants. Sensitivity analysis of regeneration energy and its three contributors is performed at several operation parameters such as absorber and stripper pressures, lean amine circulation rate, solvent concentration, reflux ratio, and CO₂ and H₂S concentrations. The results show that the heat of absorption of PZ/MDEA system is higher than that for MDEA system for the same operating conditions. The sensible heat is the main contributor in the required regeneration energy of MDEA solvent system. The simulation results have been validated against data taken from real plant and literature. The product specifications of our simulation corroborate with real plant data in an excellent approach; additionally, the profile temperature of the absorber and the stripper columns are in good agreement with literature. The overall results highlight the direction of the effects of each parameter on the heat of absorption, sensible heat, and vaporization heat.     

阿姆河气田天然气脱硫脱碳MDEA吸收塔工艺的优化

针对阿姆河气田天然气脱硫脱碳过程中MDEA吸收塔工艺落后,导致贫胺液进料量调控不精确,H_2S含量无法达到或超出设计指标的情况。应用K-SPICE软件对MDEA吸收塔进行动态模拟,在贫胺液进料环节增加了H_2S流量与贫胺液进料量的反馈调节,通过分析优化结果数据和优化前后经济性比较得出优化方案切实可行。     

天然气半贫液脱碳工艺三元胺液配方优选

为实现天然气脱碳工厂降本增效目标，基于某工厂PZ活化MDEA半贫液工艺，在现有设备能力下进一步提升胺液性能，进行三元复配胺液配方筛选以替代原有吸收剂。本文针对单一胺液的贫液、半贫液及富液分别进行实验，确定合适的主体胺液及添加剂，将胺液进行三元复配后通过实验探究三元复配胺液的吸收及再生性能，旨在寻找吸收容量大、吸收速率快、解吸率高、循环溶解度高、再生能耗低综合性能优的胺液配方。通过研究发现，单一胺液中AMP、DETA及PZ吸收性能较优，TEA再生能耗最低，解吸率最高；对于三元复配胺液而言，当MDEA/DEEA为主体胺液时，两种胺液配方贫液状态下的吸收速率和吸收负荷均较高，MDEA/TEA双主体胺液的最终解吸率高于MDEA/DEEA双主体胺液，TEA的加入显著提高了胺液的解吸率；筛选得到的三元高效胺液配方18%MDEA+18%TEA+4%PZ的半贫液循环溶解度高于原PZ活化MDEA配方，再生能耗较低，可代替PZ活化MDEA胺液应用于天然气半贫液脱碳工艺。     

MDEA-MEA混合醇胺脱硫脱碳的模拟计算

实验研究了N-甲基二乙醇胺(MDEA)和乙醇胺(MEA)混合有机胺水溶液吸收煤气中H_2S和CO_2的过程。采用严格的混合溶剂电解质理论建立了气体吸收的热力学计算模型,并用模拟计算软件(ASPEN PLUS)计算了H_2S和CO_2混合气的吸收过程,计算值和实验值符合良好。实验数据和模拟计算结果表明,采用混合醇胺脱硫具有较好的脱硫效率和选择性,符合目前工业装置对脱硫的要求。     

混合醇胺溶液吸收烟气中CO2

研究了温度、CO2含量与吸收液浓度对醇胺溶液吸收CO2性能的影响,并比较了不同复配体系对二异丙醇胺(MDEA)的活化效果。结果表明,醇胺溶液对CO2的吸收速率随反应时间的增加而降低,随吸收温度的升高而增强,以40℃为宜;吸收反应速率均随气、液相反应物含量增大而增强;混合体系对MDEA的活化效果为二乙烯二胺最好,乙醇胺最差。     

Enhancement of carbon dioxide absorption into aqueous methyldiethanolamine using immobilised activators

Blends of ‘activating’ primary or secondary amines (diethanolamine, DEA) with tertiary amines, (methyldiethanolamine, MDEA) are commonly used for the removal of CO₂ from gas mixtures. To avoid undesirable side-effects from these activators, such as increased corrosion or higher energy requirements for regeneration, we propose using immobilised primary or secondary amine groups on solid supports. In this manner the activating additives can be localised to those parts of the absorption column where the high absorption rates achieved are truly beneficial and excluded elsewhere.The studies presented were carried out to provide an initial evaluation of the feasibility of this novel concept. Preliminary experiments carried out in a discontinuously operated stirred tank reactor reveal similar enhancement of the CO₂ absorption into ‘activated’ MDEA solution, when the soluble DEA additive is replaced by a suspended solid adsorbent, containing the equivalent quantity of immobilised amine groups. Further experiments examined the CO₂ absorption in a three phase fluidised bed column. They demonstrated that the immobilised activator can be employed in a continuously operated process too.All experimental results support the basic feasibility of using immobilised primary amines in place of homogeneous additives to enhance CO₂ absorption in tertiary amine solutions.     

胺法在脱碳工艺中的应用

主要介绍了MDEA及空间位阻胺这两种高效，低耗的脱碳合成氨原料气和天然气脱碳工艺中的应用情况。