Hybrid Membrane-Cryogenic Distillation Air Separation Process for Oxygen Production

A hybrid air separation process for oxygen production uses a membrane gas permeator with bypass to increase the oxygen concentration of the feed to 23.5% before the cryogenic distillation plant. A 23.5% limit on oxygen is required to avoid use of more expensive construction materials. By pre-concentrating the oxygen, the feed flowrate to the compressor, heat exchangers and the distillation column can be reduced by 11%, which reduces power requirements and sizes of the downstream equipment. Achieving this concentration with very low energy requirements is surprisingly difficult with commercially available membranes. New membrane materials with higher fluxes and selectivities could make the process more economical.     

气源温度与解吸过程对变压吸附制氧效果的影响

研究了气源温度和解吸条件对制氧效果的影响,结果表明：细长解吸管路会导致吸附塔内氧浓度波前沿在吸附周期内极易穿透床层,在产氧期及间歇期都会有低浓度氧流入储氧罐,造成氧浓度和流量下降;较高的气源温度有利于分子筛解吸再生,在15～65 ℃内,平均每升高10 ℃,产氧体积分数可以提高1.2%。     

An investigation of reaction furnace temperatures and sulfur recovery

In a modern day sulfur recovery unit (SRU), hydrogen sulfide (H₂S) is converted to elemental sulfur using a modified Claus unit. A process simulator called TSWEET has been used to consider the Claus process. The effect of the H₂S concentration, the H₂S/CO₂ ratio, the input air flow rate, the acid gas flow of the acid gas (AG) splitter and the temperature of the acid gas feed at three different oxygen concentrations (in the air input) on the main burner temperature have been studied. Also the effects of the tail gas ratio and the catalytic bed type on the sulfur recovery were studied. The bed temperatures were optimized in order to enhance the sulfur recovery for a given acid gas feed and air input. Initially when the fraction of AG splitter flow to the main burner was increased, the temperature of the main burner increased to a maximum but then decreased sharply when the flow fraction was further increased; this was true for all three concentrations of oxygen. However, if three other parameters (the concentration of H₂S, the ratio H₂S/CO₂ and the flow rate of air) were increased, the temperature of the main burner increased monotonically. This increase had different slopes depending on the oxygen concentration in the input air. But, by increasing the temperature of the acid gas feed, the temperature of the main burner decreased. In general, the concentration of oxygen in the input air into the Claus unit had little effect on the temperature of the main burner (This is true for all parameters). The optimal catalytic bed temperature, tail gas ratio and type of catalytic bed were also determined and these conditions are a minimum temperature of 300°C, a ratio of 2.0 and a hydrolysing Claus bed.     

两段式滴管内烟煤富氧空气分级燃烧NOx排放特性研究

随着我国对大气污染物排放监管力度的日益严格,NOx控制技术已广泛应用于工业生产的各个领域。作为一种直接、简便的NOx排放控制技术,富氧空气燃烧技术已经出现在燃气锅炉和内燃发动机等行业,然而在燃煤锅炉行业中却鲜有应用。为了验证富氧空气燃烧技术在煤粉工业锅炉中的NOx减排效果,笔者以神府烟煤作为燃料,利用两段式滴管炉试验系统模拟煤粉在锅炉内燃烧的实际情况,采用热态试验方法,研究了烟煤富氧空气分级燃烧的NOx排放特性,并与单级供风、空气分级燃烧2种燃烧方式下的NOx排放情况进行对比。考察了主燃区温度、二次风配比(以主燃区过量氧气系数表示)、二次风氧浓度等关键因素对NOx排放的影响。结果表明:富氧空气分级燃烧的NOx排放显著低于单级供风燃烧,同时也低于空气分级燃烧的NOx排放。主燃区温度为1 300~1 500℃时,富氧空气分级燃烧的NOx排放减少比例比分级配风燃烧提高了6~12个百分点;富氧空气分级燃烧条件下,随主燃区温度升高,煤粉燃烧更加充分,燃料中N元素分解成NHi、HCN等大量中间产物,使主燃区气氛的还原性增强,被还原的NOx比例增加。因此,NOx排放降低且NOx排放减少比例呈现上升趋势;富氧空气分级燃烧的二次风配比对NOx排放具有显著影响,随着主燃区过量氧气系数的升高,NOx排放均呈现先降低后升高的趋势。因此存在最佳二次风配比,使NOx排放浓度最低。主燃区温度为1 300℃时,最佳主燃区过量氧气系数约为0.58;主燃区温度为1 500℃时,最佳主燃区过量氧气系数约为0.55;在主燃区过量空气系数给定的条件下,提高二次风氧浓度可以延长煤粉颗粒在主燃区的停留时间,并在煤粉颗粒表面形成局部富氧环境,促进煤粉充分燃烧,从而增强主燃区气氛的还原性,降低NOx的生成。因此,当二次风氧浓度为21%~31%时,NOx排放随二次风氧含量的升高而降低。随着二次风氧浓度的逐渐升高,NOx排放的降低趋势逐渐放缓。     

真空变压吸附捕集烟道气中二氧化碳的模拟、实验及分析

采用工业硅胶作为吸附剂,利用两塔变压吸附装置进行了烟道气变压吸附碳捕集实验。利用gPROMS软件建立两塔变压吸附模型对实验过程进行模拟,对比了实验和模拟的结果,验证了模型的准确性。通过两塔变压吸附可将15%的CO₂富集到74%,收率为91.52%。在模型基础上考察了变压吸附碳捕集过程中进料量、吸附时间、顺放压力与二氧化碳收率、纯度和能耗的关系,定性分析了吸附塔压力和进料量对压缩机能耗的影响。结果表明:增大进料量、延长吸附时间、降低顺放压力,可以有效提高产品气中CO₂浓度,但同时也导致收率的下降,前两者还会造成单位能耗的增加;吸附压力越高,进料流量越大,压缩机能耗越大。     

π型向心径向流吸附器变质量流动特性研究

对径向流吸附器内变压吸附(PSA)制氧的变质量流动规律进行研究,有助于准确掌握吸附过程及床层内的变量因素对制氧性能的影响。对π型向心径向流吸附器建立气固耦合的两相吸附模型,并对其PSA制氧过程进行了数值模拟研究,得到了床层内氧气浓度分布、温度分布以及产品气浓度的变化规律。结果表明：首次循环结束时床层内氧气最高摩尔分数可达66.02%,回收率29.2%。非稳定循环期间,氧气摩尔分数从66.02%升高至 97.5%,回收率从29.2%提高至38.5%。循环达到稳定后,床层内氧气摩尔分数最高可达98.6%,回收率38.9%左右,且达到稳定状态后床层内气固两相温差减小,逐渐达到热平衡。获得了吸附器内部气体与吸附剂两相间的传质、传热过程,为π型向心径向流吸附器用于PSA制氧提供技术支持。     

基于Aspen Plus软件的超大规模空分工艺全流程模拟

利用Aspen Plus对超大规模空分工艺进行了全流程模拟。模拟得到了气体产品和液体产品的成分、主压机和辅压机的功率及所需流量、氧气的回收率以及膨胀机所需流量,揭示了膨胀机所需流量对氧气回收率、产生的冷量以及液氧产品比例的影响。利用该模型,能够为工艺方案比选、优化设计提供模拟和预测。     

Die Primärschritte der sauerstoffinitiierten Äthylenpolymerisation

The reactions before and during the start of the oxygen initiated polymerization of ethylene have been investigated at temperatures less than 170°C, pressures up to 2200 at and oxygen concentrations in feed up to 75 ppm. The reaction suddenly starts when starting point is reached. This is caused by inhibition of the reaction by oxygen itself. The primarily radical delivering compound is formed the easier the higher the pressure is. It must be assumed that this compound decomposes more rapidly than it is produced. The amount of oxygen being consumed in not initiating side-reactions increases with its concentration in feed.     

Removal of Trace Cd2+ Using Continuous Multistage Ion Foam Fractionation: Part II—The Effects of Operational Parameters

A multistage ion foam fractionation column with bubble-cap trays was employed to study the removal of cadmium ions from simulated wastewater having low Cd concentrations (10–30 mg/L), examining the effects of foam height, air flow rate, feed flow rate, and feed Cd concentration. Sodium dodecyl sulfate (SDS) was used to generate foam in this study. An increase in foam height, which reduces liquid hold-up in the generated foam, resulted in the enhancement of the enrichment ratios of both SDS and Cd while the removal and residual factor of Cd showed insignificant change. An increase in air flow rate increased the foam generation rate, foamate volumetric ratio, and the removal efficiency of Cd but decreased the enrichment ratios of both Cd and SDS. The separation factors of both Cd and SDS decreased with increasing feed flow rate, which is mainly attributable to both the effects of the enhancement of foamate volumetric ratio and the increases in both SDS and Cd input rates. An increase in feed Cd concentration was found to increase Cd effluent concentration and SDS removal but to decrease the enrichment ratios of both Cd and SDS because of the increasing liquid entrainment in the produced foam.     

Performance of a medical oxygen concentrator using rapid pressure swing adsorption process: Effect of feed air pressure

The effects of feed air pressure on the steady‐state performance of a medical oxygen concentrator (MOC) were experimentally evaluated using a novel design of a MOC unit which produced a continuous stream of ～90% O₂ employing a rapid pressure swing adsorption (RPSA) process scheme. Dry, CO₂ free air containing ～1% Ar at different feed gas pressures was used in the tests in conjunction with a commercial sample of LiLSX zeolite as the N₂ selective adsorbent in the process. The bed size factor (BSF) can be systematically reduced by increasing the feed air pressure for any given total cycle time. The effect of feed air pressure on the oxygen recovery (R) is, however, more complex; it increases with increasing feed pressure only at longer cycle times while the effect is marginal at shorter cycle times. The BSF cannot be indefinitely reduced by lowering total process cycle time at any pressure—a minimum is exhibited in the BSF‐cycle time plot. The minimum value of the BSF decreases as the feed pressure is increased. The cycle time for the minimum BSF is, however, not significantly altered by the feed pressure in the data range of this work. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1212–1215, 2016     

Nonuniform channels in adsorbent monoliths

A model is introduced to account for nonuniform channel geometries in monolithic adsorbents. Based on nonisothermal operation, fully developed parabolic flow and the full three‐dimensional convection‐diffusion equation, the model is applied to the adsorption of dichloromethane from an air stream flowing through a binder‐less activated carbon monolith. The equilibrium parameters and the effective diffusion coefficient for adsorption are obtained independently from gravimetric adsorption experiments. The nonuniform channel model is capable of predicting breakthrough curves as a function of feed gas flow rates up to dimensionless breakthrough concentrations of about 0.4–0.6, depending on the feed flow rate. Even though the variation of effective diffusion coefficient with both concentration and temperature has been tested, successful prediction over the whole range of concentration may require the incorporation of further aspects relating to the anisotropic nature of the carbon. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Separation of glycyrrhizic acid from licorice root extract using macroporous resin

Glycyrrhizic acid (GA) is the major active ingredient of licorice which has many pharmacological activities. In the present study, separation of GA from licorice root extract has been carried out by adsorption on five different macroporous resins. Static and dynamic adsorption of GA from crude licorice root extract is studied on ion exchange resins followed by desorption. Indion 810 shows the maximum adsorption as well as desorption capacity. The adsorption experiments indicate that equilibrium can be achieved in 360 min. The adsorption equilibrium data is well fitted in the Langmuir isotherm. The separation process is optimized by investigating the effect of pH on adsorption capacity and effect of concentration of ethanol on desorption capacity. The dynamic adsorption is carried out in a column packed with Indion 810 resin and effect of feed flow rate and initial concentration of GA in extract has been studied. The results showed that increase in feed flow rate as well as initial feed concentration of GA lowers the dynamic binding capacity and mass transfer coefficient while increases the HETP. The purity of GA is increased from 14.3% to 71.5% by the dynamic desorption with 60% ethanol. Indion 810 resin can efficiently separate GA from licorice root extract with the HPLC recovery of 63.6%. This study forms the basis for large scale preparation of GA by resin adsorption.     

An Integrated Process of Olive Mill Wastewater Treatment

Abstract

Olive mill wastewater (OMWW) is considered as a challenge for environmental scientists. It is characterized by high values of total organics expressed by chemical oxygen demand (COD), biological oxygen demand (BOD₅), and phenols. In this paper, an integrated process of OMWW treatment, which includes lime precipitation, filtration using a novel technology of a membrane filter press (a pilot scale) and a post‐treatment using activated carbon adsorption for the filtrate, was studied. Lime precipitation has removed ～71% of phenols, ～39% of COD, and ～88% of BOD₅ with a rise in the total suspended solids (TSS) from 31 kg/m³ (before precipitation) to 69 kg/m³ (after precipitation).

The filtration and dewatering operation cycle is approximately 125–150 min. Filtration was examined at different feed pressure (3–5 bar), different slurry concentrations (23–69 kg/m³, dry weight), and filter aid pre‐coat with different additions of diatomite body feed. Specific cake resistance, α, was found to increase with the increase in feed pressure and to decrease with diatomite pre‐coating and slurry concentration increase. However, a further decrease in α values was obtained using diatomite body feed. Cake dewatering, via membrane squeezing, was applied using hot water (65°C) and cake moisture was dropped from ～64% before squeezing to 35% after squeezing. Twenty minutes were found enough for that stage to be accomplished. With vacuum application, for 30 min, over the hot cakes, cake moisture decreased to ～20% for cakes with an average thickness of 1 cm. The produced cakes lose more moisture by storing in open air (on the shelf), reaching an equilibrium value of 9% in 2–3 days. Calorific value of produced cake is 15.71 MJ/kg, suggesting strongly its use as an energy source. Activated carbon was used as an efficient sorbent for removing the remaining phenols and total organics from the filtrate as a post‐treatment showing promising results. Maximum removal of phenols and total organics, by lime precipitation and filtrate post‐treatment using activated carbon adsorption, reached ～99.7% and ～80%, respectively.

A process flowsheet and preliminary cost estimates are presented and compared with other processes. The thermal energy produced by the burning of the produced cakes would be enough for the thermal needs of both the olive mill plant and the proposed treatment process.     

Design of a modern automatic control system for the activated sludge process in wastewater treatment

The Activated Sludge Process (ASP) exhibits highly nonlinear properties. The design of an automatic control system that is robust against disturbance of inlet wastewater flow rate and has short process settling times is a chal enging matter. The proposed control method is an I-P modified controller automatic control system with state variable feedback and control canonical form simulation diagram for the process. A more stable response is achieved with this type of modern control. Settling times of 0.48 days are achieved for the concentration of microorganisms, (reference value step increase of 50 mg·L?1) and 0.01 days for the concentration of oxygen (reference value step increase of 0.1 mg·L?1). Fluctuations of concentrations of oxygen and microorganisms after an inlet disturbance of 5 × 103m3·d?1 are smal . Changes in the reference values of oxygen and microorganisms (increases by 10%, 20%and 30%) show satisfactory response of the system in al cases. Changes in the value of inlet wastewater flow rate disturbance (increases by 10%, 25%, 50%and 100%) are stabilized by the control system in short time. Maximum percent overshoot is also taken in consideration in all cases and the largest value is 25%which is acceptable. The proposed method with I-P controller is better for disturbance rejection and process settling times compared to the same method using PI control er. This method can substitute optimal control systems in ASP.     

Separation of methane and nitrogen using ionic liquidic zeolites by pressure vacuum swing adsorption

The separation of methane (CH₄) and nitrogen (N₂) is a significant challenge to the enrichment and utilization of low concentration CH₄ due to the similarity in the physical and chemical properties of the two molecules. In this work, we investigated the separation of CH₄ from N₂ using 100 kg of a new ionic liquidic zeolite (ILZ) material in a 6-bed pilot-scale pressure swing adsorption process. Feed gases with CH₄ concentrations of 5.0% and 16.1% were upgraded to 11.5% and 34.6%, respectively, with CH₄ recoveries higher than 80%. The pilot test results were used to anchor a numerical model that then allowed the efficient investigation of multiple operational parameters including desorption pressure and feed gas flow rates. The numerical model produced CH₄ concentrations for both product streams consistent with those measured in the pilot experiments, with root mean square deviations below 2%. The modeling results revealed that sufficiently low desorption pressures can unexpectedly lead to lower heavy product purities under limited feed gas flow conditions. Furthermore, the optimum feed gas flow rate under which maximum heavy product purity is achieved increases with lower desorption pressure. The maximum CH₄ concentrations increased from 31.8% to 41.5%, as desorption pressures decreased from 22.8 to 12.2 kPa for optimum feed flow rates between 78.2 and 105.5 mol/h. We also demonstrate a method of process optimization based on the bed capacity ratio, ℂ, which provides a scale-independent measure of the degree to which the column is being used effectively. By varying feed flow rate and/or desorption pressure, ℂ values between 0.2 and 0.8 were explored, with maxima in the combined separation performance metric (methane recovery) × (methane purity) occurring for values of ℂ in the range 0.29–0.36. This separation performance optimization by adjusting ℂ provides an effective strategy for integrating and understanding the impact of multiple operating parameters.     

Argon production from air distillation: Use of a heat pump in a ternary distillation with a side rectifier

A ternary feed mixture ABC can be separated into individual components through the use of a main distillation column with a thermally linked side rectifier. To enhance such a separation, a heat pump can be implemented to transfer heat from the condenser at the top of the side rectifier to the reboiler at the bottom of the main column. In this paper, one such heat pump is described and applied to an air distillation system separating the ternary mixture containing nitrogen, oxygen and argon. The separation is performed by a conventional double column with a crude argon side column. When this system is operated at an elevated pressure to obtain higher product pressures, the separation of oxygen and argon becomes very difficult and leads to reduced argon recovery. The proposed heat pump enhances the separation by providing a supplementary crude argon condensing duty through the vaporization of a liquid oxygen stream from the bottom of the low pressure (LP) column. This scheme improves the liquid/vapour ratio (L/V) in the bottom section of the LP column and, more importantly, increases the vapour feed to the crude argon column. This increased feed rate leads to a substantial increase in argon recovery for the elevated pressure air distillation process.     

Sweeping Gas Membrane Distillation (SGMD) as an Alternative for Integration of Bioethanol Processing: Study on a Commercial Membrane and Operating Parameters

This article considers the application of the sweeping gas membrane distillation process (SGMD) for direct separation of ethanol-water using a flat sheet PTFE membrane. It also studies the effect of operating parameters including feed concentration, feed temperature, feed flow rate, and sweeping gas flow rate on the permeation flux and selectivity of ethanol/water. The results showed that the increase in feed temperature increases in permeate flux and selectivity. Selectivities of 18.5 to 25 were achieved using dilute feeds within the temperature range of 35 to 55°C. However, by increasing the feed concentration by more than 5 wt.%, the selectivity was decreased. The increase in permeation flux and ethanol selectivity at higher feed flow rates was mainly due to the reduction of polarization effects. Moreover, the PTFE membrane was characterized by AFM. The results showed that the present process could be used as a stand-alone technique for bioethanol process integration.     

The catalytic performance of Cs-doped V/Ti/O catalysts in the oxidation of o-xylene to phthalic anhydride: a TPR/TPO and reactivity study

Titania-supported vanadia (V/Ti/O) systems were modified by addition of cesium oxide for application as catalysts in the selective oxidation of o-xylene to phthalic anhydride (PA). Catalytic tests demonstrated that cesium is a strong promoter of the activity and selectivity to PA, but this effect is evident only under well-defined reaction conditions. Samples with a Cs content lower than 0.35 wt.% Cs₂O exhibited a considerable increase in conversion as compared with the undoped V/Ti/O system. Catalytic tests made with varying o-xylene and oxygen concentrations in the feed demonstrated that in Cs-doped V/Ti/O catalysts the rate-determining step is the re-oxidation of vanadium by molecular oxygen. Thermal-programmed reduction (TPR) and thermal-programmed re-oxidation (TPO) tests evidenced that the addition of Cs decreases the vanadium reducibility and increases the re-oxidizability of the reduced vanadium sites. The positive effect of Cs on selectivity to PA was evident only for o-xylene concentrations in feed lower than 1.5 mol%.     

Optimization of Process Parameters for Spray Drying of Fermented Soy Milk

Generally used as an inexpensive source of high-quality protein with many other health-promoting properties, soy milk offers an interesting alternative when fermented. Fermentation with lactic acid bacteria brings about the value addition to soy milk, making a nutritious probiotic food product. Dehydration helps to achieve longer shelf life and easier transportation and storage, enabling wider distribution of the product. The present work pertains to optimization of process parameters for spray drying of fermented soy milk using response surface methodology (RSM). The process parameters studied include inlet air temperature, aspirator speed (air flow rate), feed flow rate, and atomization pressure. The experiments were designed using the central composite design tool. Residual moisture content was found to be low at higher inlet air temperature, lower feed flow rate, higher atomization pressure, and higher air flow rate. Porosity reduced with increased atomization pressure. Higher product yield was obtained at high air flow rate and low feed flow rate. The increase in the atomization pressure increases the cohesiveness between particles, resulting in reduced flowability. An increase in the inlet air temperature greatly reduces the viability and the isoflavone aglycone content in the product. Protein denaturation during the process was found to reduce the product solubility.     

CO〈sub〉2〈/sub〉抑制煤氧吸附过程的实验研究

煤对CO2的吸附能力较强,CO2分子会优先吸附在煤表面,减少O2的吸附量,抑制煤氧吸附过程。通过程序升温实验,研究CO2对煤氧吸附的抑制作用,测定煤样在不同CO2浓度下产生O2、CO、CH4的浓度值,分析CO2浓度对耗氧速率、CO产生率的影响规律。结果表明,37%～50%浓度的CO2对煤体耗氧速率的抑制效果明显,对煤样的CO产生率及甲烷浓度有降低作用,说明CO2能够有效抑制煤氧吸附过程,防止煤炭氧化自燃的发生。研究结果对CO2防灭火技术的开发与应用具有指导作用。