CO2 Absorption into Aqueous Solutions of Monoethanolamine,Methyldiethanolamine, Piperazine and their Blends

The removal of carbon dioxide from industrial gases, e.g. in thermal power stations to meet the discharge limits for CO₂ in flue gases, is usually achieved with a reactive absorption technique using aqueous solutions of alkanolamines. From the absorption performance point of view, primary and secondary amines are preferred. However, in case the costs of the solvent regeneration are also taken into account, tertiary amines are much more attractive. In order to combine the specific advantages of tertiary and primary/secondary alkanolamines, both types of solvents are mixed. In this paper, mixtures of monoethanolamine and methyldiethanolamine with piperazine as absorption activator are experimentally compared with respect to CO₂ removal performances at 25 °C. The absorption process in a special packed column has also been simulated with the use of published data on reaction kinetics, physicochemical properties (densities, viscosities, diffusivities, Henry coefficients) of the CO₂‐amines systems, including experimentally determined hydrodynamic and mass transfer characteristics of the CO₂ scrubber.     

活化甲基二乙醇胺溶液吸收CO2的动力学

采用圆盘塔在常压、温度３０～７０℃、ＭＤＥＡ（甲基二乙醇胺）浓度１．７５～４．２１ｋｍｏｌ／ｍ３、哌嗪浓度０．０４１～０．２１ｋｍｏｌ／ｍ３条件下，研究了活化ＭＤＥＡ吸收ＣＯ２的动力学。动力学数据证实了ＣＯ２与哌嗪之间进行着拟一级均匀［４］活化反应机理，其吸收速率可由并行拟一级快速可逆反应吸收来表示：　式中：ｋｐ＝２．９８×１０（１１）ｅｘｐ（－６４２４／Ｔ），表观活化能为５３．４１ｋＪ／ｍｏｌ。     

Absorption of Carbon Dioxide into Aqueous Xanthan Gum Solution Containing Monoethanolamine

Abstract

Carbon dioxide was absorbed into the aqueous xanthan gum (XG) solution in the range of 0–0.151 wt% containing monoethanolamine (MEA) of 0–2 kmol/m³ in a flat‐stirred vessel with the impeller of 0.05 m and agitation speed of 50 rpm at 25°C and 0.101 MPa to measure the absorption rate of CO₂. The volumetric liquid‐side mass transfer coefficient (k_La_L) of CO₂ decreased with increasing XG concentration, and was correlated with the empirical formula having the rheological behavior of XG solution. The chemical absorption rate of CO₂ was estimated by the film theory using the values of k_La_L and physicochemical properties of CO₂ and MEA. The aqueous XG solutions made the rate of absorption of CO₂ accelerated compared with the Newtonian liquid based on the same viscosity of the solution.     

Mass Transfer Modeling of SO2 into Large Water Drops

This article concerns the modeling of the SO₂ absorption and desorption by falling drops through air with low to high concentration of sulfur dioxide. In the liquid phase, a model based on local scales, interfacial liquid friction velocity and drop size diameter is used. In the continuous gas phase a more classical model is applied. Data obtained by the modeling of the SO₂ absorption and desorption by a single water drop are compared to published experimental results and a fairly good correspondence was found. On the other hand, the model shows that at high gas concentration (> 1 %) the internal resistance to diffusion dominates, while at low gas concentration (< 1000 ppb) the external resistance to diffusion dominates.     

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.     

Adsorption of SO2 on Activated Carbon for Low Gas Concentrations

Adsorption experiments of SO₂ on activated carbon has been carried out for low concentrations (about 100 ppm) at room temperature (15 to 33 °C) with varying humidity in the air. The breakthrough curves show that at high relative humidity or relative higher SO₂ concentration, the load capacity increases with respect to temperature. The humidity of the air is also of benefit to the load capacity of SO₂. When an adsorption process is interrupted and the activated carbon is kept closed for a while, the SO₂ concentration at the exit of a fixed‐bed adsorber is similar to that of the fresh activated carbon and begins at a very low value. It appears that the sorption potential has been refreshed after the storage period. Analysis of desorption experiments by simultaneous thermal analysis combined with mass spectrometry (MS) after loading, shows that the physisorbed SO₂ and H₂O are desorbed at low temperatures. At higher temperatures, the MS peak of SO₂ and H₂O occur at the same time. Compared with desorption immediately after loading, after one day, the desorption peak due to the physisorbed SO₂ disappears. From this, it can be concluded that the refreshment of the loading capacity of the activated carbon after storage is mainly due to a change in the nature of the SO₂ from a physisorbed state to a chemisorbed form. The same mechanism leads to a continuous refreshment of the sorption potential by means of a chemical reaction during the adsorption process.     

Comparison of Various Alkaline Solutions for H2S/CO2‐Selective Absorption Applied to Biogas Purification

Biogas is a common renewable energy resource. A very important stage of biogas upgrading, studied in the present work, is its purification from H₂S traces. The selective absorption of H₂S and CO₂ into oxido‐alkaline solutions containing hydrogen peroxide and into amine solutions was compared by performing absorption test runs in a cables‐bundle scrubber at 293.15 K and atmospheric pressure. The absorption rate and selectivity for H₂S over CO₂ were determined for various solute partial pressures, different alkaline absorbents and hydrogen peroxide concentrations in the scrubbing liquid, and different pH values. Higher H₂S‐selective absorption performances with oxido‐alkaline solutions than with amine solutions could be observed provided that the solution is at a low pH value (9.5) and contains a sufficient hydrogen peroxide concentration.     

Absorption of carbon dioxide into aqueous solutions of piperazine activated 2-amino-2-methyl-1-propanol

In this work, new experimental data on the rate of absorption of CO₂ into piperazine (PZ) activated aqueous solutions of 2-amino-2-methyl-1-propanol (AMP) are reported. The absorption experiments using a wetted wall contactor have been carried out over the temperature range of 298-313 K and CO₂ partial pressure range of 2-14 kPa. PZ is used as a rate activator with a concentration ranging from 2 to 8 wt%, keeping the total amine concentration in the solution at 30 wt%. The CO₂ absorption into the aqueous amine solutions is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. Parametric sensitivity analysis is done to determine the effects of possible errors in the model parameters on the accuracy of the calculated CO₂ absorption rates from the model. The model predictions have been found to be in good agreement with the experimental results of rates of absorption of CO₂ into aqueous (PZ+AMP). The good agreement between the model predicted rates and enhancement factors and the experimental results indicates that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer in PZ activated aqueous AMP solutions.     

Absorption of Carbon Dioxide into Ionic Liquid of 2-Hydroxy Ethylammonium Lactate

Abstract

Absorption of carbon dioxide into organic solvents such as DMA, NMP, DMSO, and DMF with the 2-hydroxy ethylammonium lactate (HEAL) ionic liquid was investigated using a batch stirred tank with a plane of gas-liquid interface in a range of 0–2.0 kmol/m³ of HEAL and 298–318 K at 101.3 kPa. The absorption of CO₂ was analyzed with the film model accompanied by the zwitterion mechanism of CO₂ with HEAL. The proposed model fits the experimental data of the enhancement factor due to the ready, chemical absorption of CO₂ in different solvents, temperatures, and HEAL concentrations. The reaction rate constant of CO₂ with HEAL was correlated linearly with the solubility parameter of the solvent.     

乙二胺/磷酸溶液化学吸收法烟气脱硫的研究

提出了一种有机胺吸收二氧化硫的新型烟气脱硫工艺,并建立了有机胺吸收烟气中二氧化硫的气液平衡模型,首次较好预测了二氧化硫-乙二胺-磷酸水溶液体系的气液平衡。对比0.3mol?L?1乙二胺缓冲溶液的预测结果与实验结果,最大相对偏差不超过7%。同时,以乙二胺/磷酸混合溶液作为吸收剂,在φ30mm×600mm的填料塔中进行了逆流吸收和解吸实验,确定了实验室规模下适宜的吸收工艺条件:液气比L/G=0.6~1.0L?m?3,乙二胺浓度0.3mol?L?1,吸收液初始SO2浓度4~6g?L?1,pH值6.0~7.5;解吸工艺条件为:预热温度60℃,塔釜温度103℃,喷淋密度0.7m3?m?2?h?1,富液中SO2浓度14~16g?L?1。进一步的经济分析表明,乙二胺/磷酸法脱硫费用相当于石灰石法的1/3,低于氨法和新近开发的NADS法,具有较好的经济性。     

Effect of CaSO4 Pelletization Conditions on a Novel Process for Converting SO2 to Elemental Sulfur by Reaction Cycles Involving CaSO4/CaS – Part II: Reduction of SO2 with CaS

A new process for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating secondary pollutants, developed at the University of Utah, was described in Part I of this series. In this process, sulfur dioxide is reacted with calcium sulfide to produce elemental sulfur and calcium sulfate; the latter is reduced by hydrogen to regenerate calcium sulfide. Here, in Part II, the effects of different pelletization conditions for the initial reactant calcium sulfate on the reactivity of CaS pellets produced from calcium sulfate pellets toward sulfur dioxide were studied. Experiments were performed to investigate the effects of temperature in the range 1023–1173 K, pellet size, cycle repetition, and water vapor or carbon dioxide content in the sulfur dioxide stream. The binder amount and the presence of nickel catalyst did not significantly affect the reaction rate.     

Rate-based modelling of SO2 absorption into aqueous NaHCO3/Na2CO3 solutions accompanied by the desorption of CO2

A rate-based model of a counter-current reactive absorption/desorption process has been developed for the absorption of SO₂ into NaHCO₃/Na₂CO₃ in a packed column. The model adopts the film theory, includes diffusion and reaction processes, and assumes that thermodynamic equilibrium among the reacting species exists in the bulk liquid. Model predictions were compared to experimental data from literature. For the calculation of the absorption rate of SO₂ into NaHCO₃/Na₂CO₃ solutions and concomitant CO₂-desorption, it is important to take into account all reversible reactions simultaneously. It is clear that the approximate analytical based model cannot be expected to predict the absorption rates under practical conditions because of the complicated nature of the reactive absorption processes. The rigorous numerical approach described here only requires definition of the individual reactions in the system, and subsequent solution is independent of specific assumptions made, or operational variables like pH or compound concentrations. As an example of the flexibility of this approach, additional calculations were conducted for SO₂ absorption in a phosphate-based buffer system.     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and diethanolamine

This work presents an experimental and theoretical investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and diethanolamine (DEA). The CO₂ absorption into the amine blends is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+DEA+H₂O). The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends AMP/DEA.     

SO2氧化制酸催化剂的选型及装填

介绍了SO2氧化制酸催化剂在各种不同规模、流程、原料的制酸装置上的选型和装填。催化剂的合理选型及装填是保证制酸装置正常运转的前提。     

Thermal Effects During the Absorption of CO2 in Aqueous Solutions of 3‐Amino‐1‐Propanol

In this work, we study the process of CO₂ absorption, at high partial pressures, in aqueous solutions of 3‐amino‐1‐propanol (AP), with respect to the thermal effects of this operation. All of the experiments were performed in a stirred tank gas‐liquid reactor with a flat, known interface. The variables considered were the AP concentration in the range of 0.1 to 3.0 M and the temperature within the interval of 288–313 K. From the results, we deduce that the process takes place in the instantaneous nonisothermal regime, and we propose an equation which relates the experimental results of molar flux with the initial amine concentration. At the same time, we can evaluate the temperature increase at the gas‐liquid interface.     

Ozone Solubility in Aqueous Solutions of NaCl,Na2SO4, and K2SO4: Application of the Weisenberger-Schumpe Model for Description of Regularities and Calculation of the Ozone Molar Absorption Coefficient

The ozone solubility in aqueous solutions of salts, NaCl (up to 5 М) and Na₂SO₄ (up to 2 М) and their mixtures, was studied. The results are adequately described by the semi-empirical model proposed by Weisenberger and Schumpe for calculation of the solubilities of atmospheric gases in concentrated solutions of electrolytes. By comparing the data obtained experimentally and calculated in terms of the Weisenberger and Schumpe model, the ozone molar absorption coefficient was found to be ε = 2860 ± 200 M^?1 cm^?1 at 260 nm.     

我国二氧化硫氧化制硫酸的钒催化剂现状和展望

从钒催化剂的生产、市场、开发、质量等方面分析我国二氧化硫氧化制硫酸催化剂的现状，指出我国钒催化剂与国外产品存在的差距和原因，提出发展钒催化剂的对策。     

SSXGL型高粘度管式过滤机在钛白废硫酸回收中的应用

SSXGL型高粘度管式过滤机采用自成膜工业技术,通过调节自成膜厚度达到滤液纯净度的要求,解决了以往采用陶瓷膜易堵塞、反冲洗再生困难以及采用硅藻土等预涂膜造成滤渣二次污染的问题。同时介绍了该机在钛白废硫酸浓缩工程实例中回收钛白粉的工艺流程,并分析了运行效果。     

Ti/SnO2+Sb2O3/PbO2电极在硫酸溶液中Cr3+氧化的电化学性能

对用聚合前驱体溶液通过热分解法制备的Ti/SnO2+Sb2O3/PbO2电极在硫酸溶液中Cr3+电化学氧化的电化学性能进行了研究. 分别测定了以Ti/SnO2+Sb2O3/PbO2和PbO2为阳极，硫酸介质中Cr3+电化学氧化过程的极化曲线、抗腐蚀性以及不同操作电流密度、Cr3+浓度、反应温度、硫酸浓度下的电流效率. 实验结果表明，聚合前驱体溶液通过热分解法制备的Ti/SnO2+Sb2O3/PbO2电极与PbO2电极相比具有更高的电催化活性和抗腐蚀性.