Dynamics and control of totally refluxed reactive distillation columns
杜邦 Dulux AcraTex 平整与质感饰面系统 为 Focal Point Pty Ltd R

RENDAPANEL® building panels are ‘ready-to-render’ pre-coated, mesh reinforced expanded polystyrene sheet panels manufactured and supplied by Focal Point Pty Ltd. RENDAPANEL® building panels are available in single or double mesh reinforced multi thickness 40mm, 75mm or100mm panel configurations designed for external wall cladding installations in accordance with Focal Point Pty Ltd External Insulated Cladding Systems Specifications.This coating recommendation does not constitute Dulux endorsement of this/any walling or cladding system or the suitability of building envelope / building system to meet the specific requirements of a given project.Users of this recommendation will satisfy themselves of the suitability of this substrate /coating guide / advice, relevant to their specific project long term requirements. In all cases Building System Design must conform to relevant Local / Building Codes or regulations and be in accordance with substrate supplier’s recommendations.Users must make their own determinations as to the suitability of this building system/ material relevant to their specific requirements. Design & InstallationFrame detail and panel fixing must comply with relevant Building Codes and be in strict accordance with the supplier / manufacturer’s External Insulated Cladding specifications. It is the responsibility of the Builder, Project Manager and/or Panel installer to ensure all these panels and substrate details are installed in accordance with substrate supplier recommendations, project specific engineering specification and relevant building codes prior to commencement of any coatings applications.-refer RENDAPANEL® External Insulated Cladding Technical Specifications for full design specificationsWith all cladding systems Dulux recommends that specific design advice be sought with respect to the incorporation of suitable moisture management systems. Best Practice design should incorporate a cavity drainage design and or vapour permeable sarking, suitable water diversion flashing and sealing systems relevant to the specific façade design and exposure location..General PreparationSurface must be clean and sound free of dirt, mud, grease oils or any other surface contamination. Exposed raw Expanded Polystyrene (EPS) surfaces should be sound and unaffected by weathering or UV deterioration.Good Building practice provides for expansion (movement) joints at (max.) 3M height & 6M wide intervals and at all building weak points e.g. in line with openings (window / doors), horizontally between floor levels, and at all interfaces of different building construction materials as defined by supplier / manufacturer’s and the responsible Building Engineer. The placement and correct installation of control joints is the responsibility of the Installer / Builder / Engineer relative to the construction design. Use industry approved construction grade Poly Urethane (PU) ‘paintable’- flexible Mastic as detailed by the PU manufacturer’s specifications.In accordance with RENDAPANEL® specifications, installation of 145 -160 g/m2 (minimum), 5 x 5 mm aperture, Alkali Resistant reinforcement mesh across all panel joints, raw EPS surfaces, at external and internal corners, edge reveals, and at diagonals across corners of all window and door openings if no movement joints are installed.- refer RENDAPANEL®External Insulated Cladding Technical Data for full design specification.Joint Reinforcement mesh will be imbedded in a basecoat of RenderWall P400, prior to installation of a final levelling application of Dulux RenderWall P400. - r efer Coating System section for mix instructions and installation guidelinesIndustry Best practice recommends a full mesh application using Reinforcement Mesh that is suitably accredited Alkali Resistant Fibreglass with a nominal 5mm X 5mm weave and a mass weight of not less than 165 gsm/M2.All reinforcing mesh is overlapped by a minimum of 100mm on installation.The installation of additional strips across joints, external and internal corners, edge reveals, and at diagonals across corners of all window and door openings is also recommended.Avoid the finishing of these Claddings Systems with dark colours - these may raise the surface temperature of the EPS and damage the cladding system. Use colours with a LRV greater than 35% or consult Dulux on the potential to use DULUX InfraCOOL Heat Reflective Coatings that will keep the surface cooler.Project Duspec DULUX AcraTex RenderWall P400 Levelling & Texture Finishing System for Rendapanel.Project ID Principle Focal Point Duspec no. Page no. 1 of 3Issue Prepared By Issue 3 Prepared By Shane LangkildeDate Approved By Date 20.10.2015 Approved ByDISCLAIMER:Any advice, recommendation, information, assistance or service provided by any of the divisions of DuluxGroup in relation to goods manufactured by it or their use and application is given in good faith and is believed by DuluxGroup to be appropriate and reliable. However, any advice, recommendation, information, assistance or service provided by DuluxGroup is provided without liability or responsibility PROVIDED THAT the foregoing shall not exclude, limit, restrict or modify the right entitlements and remedies conferred upon any person or the liabilities imposed upon DuluxGroup by any condition or warranty implied by Commonwealth, State or Territory Act or ordinance void or prohibiting such exclusion limitation or modification. Coating systems can be expected to perform as indicated on the DuspecBasecoat & Reinforcement Mesh – Surface Levelling Data Sheet Base Layer Min.Cover P400 RENDERWALL BASE COAT WITH EXSULITE REINFORCEMENT MESHIn a clean 15 litre pail add 3.5-4.0 litres of clean water slowly add RenderWall P400while stirring till a cream trowel able paste is formed.Apply the basecoat layer of RenderWall P400 by stainless steel trowel to fully cover the EPS surface with a 2-3 mm (min.) basecoat. Whilst wet embed the Reinforcing mesh into the RenderWall P400 and overlapped all edges by a minimum of 100mm.Note: The mesh is not to be pushed through the wet render onto the face of the Exsulite Panel. AUDA1596RenderWallP400(1.7kg/m2/mm)Assuming no loss+Alkali resistantFibre Glassmesh165 gm weight(minimum.)5 x 5 mmaperture2 -3mmwet on wetDULUX AcraTex RenderWall P400 Finishing coatApply finishing coat of RenderWall P400 basecoat mixture to completely cover andencapsulate the mesh with a minimum of 2mm cover. Finish the RenderWall P400 base coat by lightly scratching the surface to provide a surface “key” for subsequent levelling or texture coats.Note: A minimum 4mm-5mm cover of RenderWall P400 to the EPS Panel once dried.AUDA1596RenderWallP4001.7kg/m2/mm)Assuming no loss3 mm16 hoursWHERE ADDITIONAL IMPACT RESISTANCE & OPTIONAL LEVELLING COAT IS REQUIRED Where additional impact resistance is required apply and embed an additional Exsulite reinforcement mesh layer coat of P400 RenderWall as specified or directedAdd RenderWall P400 to fresh water to form trowel able paste. Apply by hawk and trowel or render pump over the Base Coat application. Screed and float level Finish by polystyrene or wood float to a suitable level finish for subsequent Texture Coating AUDA1596RenderWallP4002-3mm16 hours Data Sheet. Application rate RecoatPRIME COAT : DULUX AcraTex – AcraPrime 501/1 L/Shade 194-20809 Optional : but recommended during hot weatherThe use of AcraPrime consolidates and conditions the surface and enhances subsequent coating application and total system durability.Apply by conventional roller method evenly over the surface AUDA044110 sq mper litre4 hoursTEXTURE COAT : DULUX AcraTex – Coventry Coarse L/Shade 194-85944Apply with Hawk & Trowel evenly over surface to the thickness of the largest particles. Follow up with a light ‘floating’ process to level out the product using red plastic trowel/float. AUDA10650.8 sq m2per litre8 hoursSHIELDCOAT : DULUX AcraTex AcraShield Matt L/Shade 194-X0100 (HiOP) Apply with a medium nap roller over the surface ensuring a wet edge is maintained over theapplication area.Dulux recommends 2 coats applications for even coverage to minimising “cutting in” and “lap mark” effects. Where 2 coats are applied, dilute the first coat with 10% water.AUDA14095 m2per Litreper Coat4 hoursProtectfrom rainin first 16hoursSHIELDCOAT : DULUX AcraTex AcraShield Matt L/Shade 194-X0100 (HiOP) Apply with a medium nap roller over the surface ensuring a wet edge is maintained over theapplication area.Dulux recommends 2 coats applications for even coverage to minimising “cutting in” and “lap mark” effects. AUDA14095 m2per Litreper CoatProtectfrom rainin first 16hoursProject Duspec DULUX AcraTex RenderWall P400 Levelling & Texture Finishing System for Rendapanel.Project ID Principle Focal Point Duspec no. Page no. 2 of 3Issue Prepared By Issue 3 Prepared By Shane LangkildeDate Approved By Date 20.10.2015 Approved ByDISCLAIMER:Any advice, recommendation, information, assistance or service provided by any of the divisions of DuluxGroup in relation to goods manufactured by it or their use and application is given in good faith and is believed by DuluxGroup to be appropriate and reliable. However, any advice, recommendation, information, assistance or service provided by DuluxGroup is provided without liability or responsibility PROVIDED THAT the foregoing shall not exclude, limit, restrict or modify the right entitlements and remedies conferred upon any person or the liabilities imposed upon DuluxGroup by any condition or warranty implied by Commonwealth, State or Territory Act or ordinance void or prohibiting such exclusion limitation or modification. Coating systems can be expected to perform as indicated on the DuspecCoatings should be applied in full accordance with relative product Technical and Application Data Sheets. This system is recommended where panel misalignment is NOT greater than 4mm.Practical spreading rates will vary from quoted theoretical figures depending on substrate porosity, surface roughness, overspray losses, application methods and environmental conditions (e.g. wind).All preparation and painting must conform to AS2311: The Painting of Buildings:-Plan for application to shaded surfaces, avoid hot windy condition or where rain is likely.Do not apply products in direct sunlight or if the Relative Humidity is above 85% or temperature is within 3°C of Dew Point orwhere the surface temperature is greater than 30°C or below 10°C, or likely to fall below 10°C during the application or dryingperiod. Allow longer times under cool, moist, or still conditions and or when applied at high film builds. Protect from dew, rain andfrost for 48 hours when applying at the recommended spread rate.Avoid application in hot, windy conditions or on hot surfaces cool the surface by hosing with water and paint the cool dampsurface.When using Bright Reds, Oranges, Blues and Yellows or where very light colours are applied over highly contrasting colours anextra coat maybe required. Application techniques should be adjusted to achieve the recommended DFT and finishing standard.To avoid "Picture Framing" of ‘high build’ texture topcoats use only a ‘wet on wet’ cutting-in & coating technique incorporatingmasking taping of the perimeter of the application section.When the Applicator is preparing the site sample for approval he should advise the Project Superintendent if the substratecondition is not of sufficient standard to produce the specified finish. At commencement of coating system application to thesubstrate it shall be deemed that the Applicator has certified that the surface which it is to be applied to is fit to receive thespecified coating(s) system.COLOUR -It is recommended to avoid Dark colours on critical large wall elements where the resultant higher surfacetemperatures generated may increase thermal expansion and contraction stress - Use colours with a Light Reflectance Value(LRV) greater than 35% &/or consult Dulux regarding the potential to use InfraCOOL Heat Reflective Coatings that may keepsurfaces cooler.LOCATION - The coastal area is considered a marine environment and as such salt potentially can shorten the life of the coating systems. Care needs to be taken to wash down all areas twice. Once to remove surface contaminants, and raise salts to thesurface and then secondly to remove these salts. Due to the locality, Weather conditions and lag time between applications ofthe coating system it may require the need to wash again, between coats.GLANCING LIGHT - Joints and panel deformation may be clearly evident under glancing light, casting visible shadows of theminute and uneven projections of the joints. Glancing light is light that is nearly parallel to the surface of the wall and casts visible shadows and uneven projections of the joints. Just like rendered masonry/ Jointed system any uneven projections will behighlighted and as such are outside the control / scope of this specification.The dynamics of the substrate is outside the control of Dulux Australia and as such joint deformation or cracking is excluded from warranty terms. Refer warranty document for full terms and conditions.This specification is to be read in conjunction with DULUX product data sheetsWhen using this specification, the Installer shall maintain adequate records of proof or purchase and use of Dulux AcraTexProductsA DULUX warranty can only be provided when the full AcraTex system is applied by a DULUX AcraTex trained applicator, according to specification at the specified spreading rates, & to the surface preparation details described in the DULUX AcraTex Specification Manual. Project Duspec DULUX AcraTex RenderWall P400 Levelling & Texture Finishing System for Rendapanel.Project ID Principle Focal Point Duspec no. Page no. 3 of 3Issue Prepared By Issue 3 Prepared By Shane LangkildeDate Approved By Date 20.10.2015 Approved ByDISCLAIMER:Any advice, recommendation, information, assistance or service provided by any of the divisions of DuluxGroup in relation to goods manufactured by it or their use and application is given in good faith and is believed by DuluxGroup to be appropriate and reliable. However, any advice, recommendation, information, assistance or service provided by DuluxGroup is provided without liability or responsibility PROVIDED THAT the foregoing shall not exclude, limit, restrict or modify the right entitlements and remedies conferred upon any person or the liabilities imposed upon DuluxGroup by any condition or warranty implied by Commonwealth, State or Territory Act or ordinance void or prohibiting such exclusion limitation or modification. Coating systems can be expected to perform as indicated on the Duspec。
富水软弱围岩隧道全断面帷幕注浆变形机理及控制研究

河南科技Henan Science and Technology交通与土木工程总第873期第2期2024年1月收稿日期:2023-12-15作者简介:王荣飞(1965—),男,本科,高级工程师,研究方向:结构设计。
富水软弱围岩隧道全断面帷幕注浆变形机理及控制研究王荣飞(镇江市规划勘测设计集团有限公司,江苏镇江212004)摘要:【目的】为进一步揭示富水软弱围岩隧道全断面帷幕注浆浆液扩散规律以及地层加固、防渗止水原理。
【方法】以莞惠城际GZH-4标暗挖隧道穿越人工湖底全风化岩层为工程背景,通过现场取样及数值计算分析,对全断面帷幕注浆隧道的掌子面变形、岩层取芯率、地层水平收敛及地表沉降等进行探讨,深入分析隧道帷幕注浆浆液扩散规律及地层加固、防渗止水原理。
【结果】结果表明:注浆浆脉构成的浆脉骨架可与周围岩体相黏接形成结石体,能有效提高岩体强度及地层抗渗透性能;高压注浆导致掌子面易于鼓胀或开裂,精准控制注浆初始条件和超前预测,可有效避免这一现象的发生;隧道的全断面帷幕注浆可增强岩体自承载能力,能有效抑制隧道的水平净空收敛变形;全断面帷幕注浆对富水软弱地层隧道开挖时的地表沉降有很好的抑制作用。
【结论】研究成果揭示了富水软弱围岩隧道全断面帷幕注浆的变形机理,并提出了相应的控制方法,可为类似地质环境下岩体注浆提供理论支撑与技术指导。
关键词:富水软弱围岩;隧道全断面帷幕注浆;加固地层;防渗止水中图分类号:TU94+1文献标志码:A文章编号:1003-5168(2024)02-0052-07DOI :10.19968/ki.hnkj.1003-5168.2024.02.010The Deformation Mechanism and Control of Full-Section CurtainGrouting in Tunnels with Rich Water and Weak Surrounding RocksWANG Rongfei(Zhenjiang Planning Survey and Design Group Co.,Ltd.,Zhenjiang 212004,China)Abstract:[Purposes ]In order to further elucidate the diffusion law of grouting fluid and the mechanismof ground reinforcement and water stopping in the full section curtain of a tunnel with rich water andweak surrounding rock.[Methods ]Taking the GZH-4mined tunnel crossing the artificial lake bottomfully weathered rock layer in the Guan-Hui intercity as the background,the deformation of the tunnel face,the rate of core recovery,the horizontal convergence of the strata,and the surface subsidence were studied through on-site sample and numerical calculation analysis.In-depth analyses were done of the stratum reinforcement,water sealing,and the grouting slurry´s diffusion law.The corresponding preven⁃tive measures were proposed.[Findings ]The results show that the grouting veins´framework could unite with the nearby rock to form a stone body,which significantly increased the strength and permeability of the formation.High-pressure grouting caused the tunnel face to swell or crack.This phenomenon could be effectively avoided by precisely managing the initial grouting conditions and forecasting in advance.The full-section grouting of the tunnel could enhance the self-bearing capacity of the rock mass and ef⁃fectively suppress the horizontal clearance convergence of the tunnel.[Conclusions ]The results of thisstudy reveal the deformation mechanism of full-section curtain grouting in tunnels with rich water and weak surrounding rocks and propose corresponding control methods that can provide theoretical support and techni⁃cal guidance for rock mass grouting in similar geological environments.Keywords:water-rich and weakly fractured rock mass;full-section curtain grouting of the tunnel; strengthening the formation;impermeability performance0引言由于富水软弱破碎岩体的不稳定性,其在地下工程尤其是隧道工程的施工中具有极大的工程风险隐患。
伏诺拉生联合贲门缩窄术治疗重度反流性食管炎的效果评估

伏诺拉生联合贲门缩窄术治疗重度反流性食管炎的效果评估*张静智① 曾玲① 刘雪① 叶鹏① 石柳① 温建军① 【摘要】 目的:探讨伏诺拉生联合贲门缩窄术治疗重度反流性食管炎(RE)的临床效果。
方法:选取赣州市人民医院2021年6月-2022年8月收治的60例重度RE患者,根据随机数字表法将患者分为对照组(30例)、观察组(30例);对照组采用雷贝拉唑+贲门缩窄术治疗,观察组采用伏诺拉生+贲门缩窄术治疗;对比两组临床症状评分[胃食管反流病问卷(GerdQ)]、食管动力学指标[食管远端收缩积分(DCI)]、上食管括约肌压力(UESP)、卧位反流时间百分比(PRRT)及下食管括约肌压力(LESP)]、24 h酸反流、食管黏膜愈合及复发情况。
结果:治疗1个月,观察组GerdQ评分较对照组低,差异有统计学意义(P<0.05);治疗1个月,观察组LESP较对照组高,PRRT较对照组低,差异均有统计学意义(P<0.05);两组治疗前、治疗1个月DCI、UESP对比差异均无统计学意义(P>0.05);治疗1个月,观察组反流次数较对照组低,最长反流持续时间均较对照组短,差异均有统计学意义(P<0.05);观察组食管黏膜总愈合率较对照组高,复发率较对照组低,差异均有统计学意义(P<0.05)。
结论:重度RE患者采用伏诺拉生联合贲门缩窄术治疗可减轻临床症状,改善食管动力学,减少24 h酸反流情况,促进食管黏膜愈合,降低复发率。
【关键词】 反流性食管炎 伏诺拉生 贲门缩窄术 食管动力学 食管黏膜愈合 Evaluation of the Efficacy of Vonoprazan Combined with Cardial Constriction Surgery in the Treatment of Severe Reflux Esophagitis/ZHANG Jingzhi, ZENG Ling, LIU Xue, YE Peng, SHI Liu, WEN Jianjun. //Medical Innovation of China, 2023, 20(21): 034-038 [Abstract] Objective: To explore the clinical efficacy of Vonoprazan combined with cardial constriction surgery in the treatment of severe reflux esophagitis (RE). Method: Sixty patients with severe RE admitted to People's Hospital of Ganzhou City from June 2021 to August 2022 were selected and divided into control group (30 cases) and observation group (30 cases) according to random number table. The control group was treated with Rabeprazole + cardial constriction surgery, while the observation group was treated with Vonoprazan + cardial constriction surgery. The clinical symptoms scores (GerdQ), esophageal motility indexes [distal esophageal constriction score (DCI), upper esophageal sphincter pressure (UESP), percentage of recumbent reflux time (PRRT) and lower esophageal sphincter pressure (LESP)], 24-hour acid reflux, esophageal mucosal healing and recurrence were compared between the two groups. Result: After one month of treatment, the GerdQ score of the observation group was lower than that of the control group, the difference was statistically significant (P<0.05); after one month of treatment, the LESP of the observation group was higher than that of the control group, and PRRT of the observation group was lower than that of the control group, the differences were statistically significant (P<0.05); there were no statistically significant differences in DCI and UESP between the two groups before and after 1 month of treatment (P>0.05); after one month of treatment, the frequency of reflux in the observation group was lower than that in the control group, and the longest duration of reflux was shorter than that in the control group, with statistically significant differences (P<0.05); the total healing rate of the esophageal mucosa in the observation group was higher than that in the control group, and the recurrence rate was lower than that in the control group, with statistically significant differences (P<0.05). Conclusion: The combination of Vonoprazan and cardial constriction surgery can alleviate clinical symptoms, improve esophageal dynamics, reduce 24-hour acid reflux, promote esophageal mucosal healing, and reduce recurrence rate in patients with severe RE.*基金项目:江西省卫生健康委科技计划项目(202212464)①江西省赣州市人民医院 江西 赣州 341000通信作者:张静智 反流性食管炎(RE)作为临床常见的胃食管反流病,其多因食管清除能力下降、黏膜防御屏障降低等因素导致,容易引起烧心、上腹痛等症状,影响患者日常生活[1]。
超重力微乳液吸收处理餐饮业油烟的实验研究

2019年 第6期 广 东 化 工 第46卷 总第392期 · 87 ·超重力微乳液吸收处理餐饮业油烟的实验研究曲天煜1,曲奕安2,焦奕翔2(1.中国石油炼油与化工分公司安全环保处,北京 100007;2.北京师范大学附属第二中学,北京 100088)[摘 要]针对餐饮业油烟组分复杂、浓度波动大等问题,开展了超重力微乳液吸收处理餐饮业油烟的实验研究,取得了良好效果。
实验结果表明:废气中油烟浓度为10.5~15.2 mg/m 3,在超重力因子为187~250、进气量为6~8 m 3/h 、液气比为1.5~2.0 L/m 3的条件下,微乳液对油烟吸收率最高可达93 %,处理装置出口废气中油烟浓度<1.0 mg/m 3,满足国家排放标准要求(<2.0 mg/m 3)。
[关键词]餐饮业油烟;吸收;超重力;微乳液[中图分类号]TQ [文献标识码]A [文章编号]1007-1865(2019)06-0087-03Experimental Research of Cooking Oil Fume by Micro-emulsion Adsorption on theCondition of Hyper-gravityQu Tianyu 1, Qu Yi’an 2, Jiao Yixiang 2(1. HSE Department, Refining & Chemicals Company, Petro China, Beijing 10007; 2. The Second High School Attached To Beijing Normal University, Beijing 100088, China)Abstract: According to the problem on treatment of cooking oil fume such as complex compound and concentration fluctuation, experimental research of cooking oil fume by micro-emulsion adsorption on the condition of hyper-gravity was accomplished. The result showed that when concentration of cooking oil fume was from 10.5mg/m 3 to 15.2 mg/m 3, the max adsorption ratio of micro-emulsion to cooking oil fume could be 93 % on the condition of hyper-gravity factor 187~250, waste gas inlet 6~8 m 3/h, ratio of liquid to gas 1.5~2.0 L/m 3. Concentration of cooking oil fume in outlet was less than 1.0 mg/m 3, so national standard (less than 2.0 mg/m3) could be fully met.Keywords: cooking oil fume ;adsorption ;Hyper-gravity ;Micro-emulsion近年来,餐饮业油烟污染日益引起社会和公众的重视。
constructionandbuildingmaterials

constructionandbuildingmaterialsBehavior and mix design development of concrete made with recycled aggregate from deconstructed lead-contaminated masonry materialsJ.Hu a ,?,K.Wang b ,J.A.Gaunt ba Department of Engineering Technology,Texas State University-San Marcos,San Marcos,TX 78666,United StatesbDepartment of Civil,Construction and Environmental Engineering,Iowa State University,Ames,IA 50011,United Statesa r t i c l e i n f o Article history:Available online xxxx Keywords:Aggregate Cement Concrete Lead Masonry Nomograph Recycleda b s t r a c tThe present study is to develop an effective method for using deconstructed,lead-contaminated masonry materials in new concrete so as to minimize the environmental impact,cost,and time of the deconstruc-tion.The approach to this method is to use crushed masonry materials to replace natural aggregate in conventional concrete.Two different types of masonry materials (concrete blocks and clay bricks)were collected,painted with lead-based paint (LBP),and then crushed to simulate recycled LBP-contaminated masonry materials.Three types of cement (type I Portland cement,Calcium Sulfoaluminate (CSA)cement,and Portland cement with 5%phosphate addition)were selected for sequestering lead in the recycled aggregate.A concrete mix design matrix was developed with different water-to-cement ratios (w/c),aggregate-to-cement ratios (a/c),types of cements,and types of masonry materials.Based on the test results,mix design nomographs were developed for concrete made with the recycled,LBP-contaminated masonry materials.The results indicate that the lead can be sequestered,or rendered non-leachable,due to the high alkalinity of cement.The concrete therefore no longer has the toxicity characteristic for lead and is suitable for various types of new construction,such as foundation and pavement,reinforced beams,columns,and walls.ó2012Elsevier Ltd.All rights reserved.1.IntroductionIn the United States,many masonry structures built before 1980s contain lead-based paint (LBP),which causes a considerable environmental and health concern.Both the US Environmental Protection Agency (EPA)and the Occupational Safety and Health Administration (OSHA)have established regulations governing the management of LBP in buildings.Deconstruction of these struc-tures is often time consuming and costly due to the paint removal and the hazardous material disposal [1–3].Clearly,a more cost effective,environmentally friendly method is urgently needed for remediating and reusing deconstructed masonry materials con-taminated with LBP.From a chemical point view,the degree of the hazard resulting from LBP is often de?ned by the solubility of lead in a material.The solubility of lead in a material is generally controlled by the pH or alkalinity of the material.The Eh–pH diagram for an aqueous lead-carbonate system indicates that lead will be insoluble if the system has a pH value above 6or 7[4–6].In a cement-based material,the pH values of pore solutions often range from 11to 13,thus possi-bly sequestering lead in the material.Using the above-mentioned concept,a study has been con-ducted to sequester lead by recycling the lead-contaminated deconstruction masonry materials as concrete aggregate.A key of this study is to design rational mix proportions so that the concrete cannot only sequester lead in the recycled aggregate but also meet general concrete construction and structural performance require-ments,such as having proper workability and strength.This paper presents a rational mix design method for proportioning non-hazardous,well-performing,sustainable concrete utilizing the recycled,lead-contaminated aggregate for ?eld construction.The mix design development includes three major steps:(1)characterizing the recycled masonry materials –evaluating their toxicity,speci?c gravity,absorption,and strength,(2)proportion-ing concrete mixtures based on workability control –designing concrete mixtures to have low,medium and high slumps so as to permit the concrete to be used for different construction applica-tions,and (3)performance evaluation –examining the lead leach-ing ability or sequestering effectiveness and strength of the concrete containing recycled,lead-contaminated deconstruction masonry materials.As a result,a series of mix design nomograms are established that illustrate the relationships between the mix proportion parameters (such as water-to-cement ratio,aggre-gate-to-cement ratio,and cement content)and concrete perfor-mance (such as lead sequestering effectiveness and strength).0950-0618/$-see front matter ó2012Elsevier Ltd.All rights reserved.doi:10.1016/j.conbuildmat.2011.07.067Corresponding author.Tel.:+15122456328;fax:+15122453052.E-mail address:jiong.hu@/doc/0fc77951804d2b160b4ec0fb.html (J.Hu).prepared (Table 2).Air entraining agent with the recommended dosage was used in all of the concrete mixes studied.2.3.Test methodsPhysical properties of the masonry materials were characterized,and their total and leachable lead contents were evaluated.The speci?c gravity and absorption of the crushed masonry materials were measured according to ASTM C127and ASTM C128.Sieving analysis and bulk density (unit weight)tests were conducted for the painted and crushed masonry materials according to ASTM C136,and ASTM C29respectively.The leachability of lead from the LBP-painted recycled aggregates and the concrete mixes made with those aggregates was tested using the Toxicity Characteristic Leaching Procedure (TCLP),EPA Method 1311[9].The total lead con-tent in the materials was also evaluated using the California Waste Extraction Test (WET)[10].Concrete was mixed based on the ASTM C192multiple-step mixing procedure.The slump of fresh concrete was measured according to ASTMC143immediately after mixing.In this study,the slump test was not only a measurement to evaluate the workability of concrete,more importantly,the slump value was used as a con-trol parameter for concrete mix design.Different slumps are required for different concrete construction applications.Concretes with three different ranges of slumps were designed:(1)25–50mm slump for low workability concrete (generally used for pavements and slabs),(2)75–100mm slump for medium workability concrete (generally used for beams,walls,columns,reinforced concrete),and (3)150–175mm slump for high workability concrete (generally used for heavily reinforced components with complicated shapes).The entire sample preparation and curing process followed ASTM C192.Compressive strength of hardened concrete was tested at the age of 3,7and 28days according to ASTM C39.The broken specimens from compression testing were further processed and then used for the TCLP soluble and total lead content (WET)tests.3.Results and discussion3.1.Characterization of recycled,LBP-contaminated aggregate Table 3presents the physical properties and lead content of the lead-contaminated masonry materials used.The test results indi-Table 1Oxide and chemical composition of cement (%).CaOSiO 2Al 2O 3Fe 2O 3MgO SO 3TiO 2Oxide composition (%)Portland cement 62.9620.96 4.54 3.48 2.91 2.77–CSA cement40.00 5.5537.50 1.50 1.7510.00 1.25C 3SC 2S C 3A C 4AF Gypsum Ca 4Al 6O 12SO 4Chemical composition (%)Portland cement 53.7119.58 6.1410.590.78–CSA cement0.4212.5910.64–1.0773.37Fig.1.Painting with LBP.Fig.2.Crushing of LBP contaminated masonry materials.cated that the recycled masonry materials had lower speci?c grav-ity (2.34–2.39)than natural aggregate (2.5–2.9),while the absorp-tion of the recycled aggregate (5.11–7.11%)was much higher than natural aggregate (0.2–4.0%)[11,12].The void contents of the four(a) Masonry A (b) Masonry BTable 2Concrete mix proportions.CementMasonry a/c w/c C (kg/m 3)Cement Masonry a/c w/c C (kg/m 3)1Portland A 3.00.2850025Portland C 6.00.362662Portland A 3.00.3145626Portland C 6.00.422653Portland A 3.00.3247727Portland C 6.00.442554Portland A 4.50.3234828Portland D 3.00.394835Portland A 4.50.3433029Portland D3.00.434756Portland A4.50.3732130Portland D 3.00.484367Portland A 6.00.3426531Portland D 4.50.503408Portland A 6.00.3626632Portland D4.50.523299Portland A 6.00.4125433Portland D 4.50.5633410Portland B 3.00.3450634Portland D 6.00.5626711Portland B 3.00.3547135Portland D 6.00.6025712Portland B 3.00.4047336Portland D 6.00.7425313Portland B 4.50.3935137CSA B 3.00.4546814Portland B 4.50.4231838CSA B4.50.4635415Portland B 4.50.4831739CSA B 6.00.5026916Portland B 6.00.4526940CSA D 3.00.4647017Portland B 6.00.4825641CSA D4.50.5134918Portland B 6.00.5523642CSAD 6.00.6126519Portland C 3.00.3049943Phosphate B 3.00.3748320Portland C 3.00.3348644Phosphate B 4.50.4134921Portland C3.00.3647545Phosphate B 6.00.4925322Portland C4.50.3333946Phosphate D 3.00.4347323Portland C 4.50.3634447Phosphate D 4.50.5333624 PortlandC4.50.3933448PhosphateD6.00.62263Note :Here,a/c is aggregate-to-cement ratio;w/c is water-to-cement ratio;and C is cement factor.J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxx3and 10.1g/Kg,larger than 1g/Kg,which shall be de?ned as hazard materials based on the California regulation.masonry C and D had TCLP lead content of 142and 77mg/L and the total lead content from WET tests of 12.5and 5.82g/Kg,which were de?ned as haz-ard materials based on both the RCRA and California regulations.The critical issue in the present study is to ?nd out whether or not the concrete made with these hazard materials still have tox-icity characteristic.3.2.Lead content and lead leachability of concreteThe above mentioned lead-contaminated masonry materials were crushed and used as aggregate in the concrete mixes as de-signed in Table 1.The TCLP lead,TCLP pH and total lead of the 48designed mixes were determined at the concrete age of 28-days.Results of compressivestrengths,together with lead content and lead leachability of all 48mixes can be found in Table 4.Detailed test results and analysis can be found in Wang et al.[8].Fig.5presents the TCLP pH value and leachable Pb content of concrete mixes studied.Although the total lead in the concrete mixes were high (up to 2.2%),the ?gure shows that all concrete mixes studied,except four mixes with masonry material D,had TCLP leachable Pb content less than1mg/L,much lower than the RCRA limit of 5mg Pb/L.As a result,these concrete mixes are con-sidered as nonhazardous materials under RCRA although their aggregate is hazardous.The four mixes that showed hazard charac-teristic were mixes 34and 36(Table 1),which had a high a/c(6.0)and low Portland cement content (267and 253kg/m 3)and mixes 40and 42,which was made of CSA cement with a/c of 6.0and3.0respectively.The result is probably due to the fact that the CSA cement was less alkaline than Portland cement,and the con-crete made with CSA cement had lower pH values than the corre-sponding concrete made with Portland cement,thus being less effective for sequestering lead in the concrete.A mix design withhigher cement content or high alkaline cement may be used to in-crease the alkalinity of the concrete and reduce its TCLP Pb value.Addition of5%phosphate in Portland cement did not signi?-cantly change the TCLP lead concentrations and total lead in the concrete.It is believed that if highly insoluble hydroxypyromorph-ite [Pb 5(PO 4)3OH]was formed in the concrete system through the lead phosphate reaction,it would have sequestered lead from the highly acidic conditions of the total lead test.This might have sug-gested a means for rendering LBP-contaminated masonry nonhaz-ardous under California law.This reaction,however,did not occur in the present study.The concentrations of phosphate added ran-ged from 31%to 62%of the amounts needed to stoichiometrically convert the lead in the concrete to hydroxypyromorphite but did not result in proportionate reductions in detectable total /doc/0fc77951804d2b160b4ec0fb.html pressive strength of concreteCompressive strength of all concrete mixes was tested at ages of 3days,7days,and 28days.Fig.6illustrates the effects of materials and mix parameters on the concrete strength.The trends of the ef-fects were similar for the concrete at three different testing ages.Generally,concrete strength decreased with increased water-to-cement ratios (w/c)and aggregate-to-cement ratios (a/c).As observed in Fig.6,for a given w/c,masonry B and D resulted in higher concrete strength than masonry A and C,which is prob-ably related to the concrete workability and strength of the recy-cled aggregate,respectively.For a given mix proportion,concrete made with CSA cement provided higher early age compressive strength than the corresponding concrete made with Portland ce-ment.The large strength and workability ranges imply that,with appropriate design,the concrete made with recycled aggregate from deconstructed masonry materials can be used for variousTable 3Physical properties and lead content of lead-contraindicated masonry materials.Concrete blocks Clay bricks AB C D Speci?c gravity 2.34 2.39 2.37 2.39Absorption (%)7.70 5.95 6.52 5.11Voids between aggregate particle (compacted)(%)36.7937.2041.3239.92Voids between aggregate particle (uncompacted) (%)38.5241.9847.746.33Compressive strength (MPa)21.0732.7973.65101.53TCLP pH6.737.02 5.11 4.88TCLP Pb,mg/L (toxicity limit:5mg/L) 4.17 1.2914277WET Total Pb,g/Kg (toxicity limit:1g/Kg)15.410.112.55.82Note :The underlined values indicate that these materials are classi?ed as toxic materials based on RCRA or California regulations.4.Gradation of the aggregate recycled masonry materials studied.(Note:DOT-C3and C4are natural aggregate used for conventional pavement concrete USA)types of constructions,such as foundation,pavement,reinforced beams,columns,and walls.A cost effective analysis by the authorsshowed that a signi?cant saving can be achieved by using LBP-con-taminated masonry materials as recycled aggregate in concrete.The cost savings may result from eliminating LBP removal and waste material disposal,which will minimize the use of secure land?lls,eliminate the time and equipment required for sieving and re-grading recycled aggregate,and reduce natural aggregate consumption for concrete construction.Details of this cost effec-tive analysis can be found in a separated publication [13].4.Mix design nomograph developmentIn the present study,a nomograph was developed for concrete made with each type of recycled,LBP-contaminated aggregate and/doc/0fc77951804d2b160b4ec0fb.html ing the mix design nomograph,proper mix propor-tions can be selected for the desired workability and strength.The nomograph combines three relationships developed for the prop-erties of fresh and hardened concrete into one graph.The mix de-sign nomograph uses three correlations:Abrams’law,Lyse’s law,and Molinari’s law [14,15].Abrams’law correlates the compressive strength of concrete with the w/c as:f 0c ?k 1k w =c2e1Twhere k 1,and k 2are constants depending on the materials used.Lyse’s law correlates the water-to-cement ratio (w/c)with the aggregate-to-cement ratio (a/c)(by weight)as:ea =c T?k 3ew =c Ttk 4e2Twhere a/c is the aggregate-to-cement ratio,k 3,and k 4are constants depend on the materials used.Molinari’s law correlates the cement content and aggregate-to-cement ratio as:C ?1000k 5ea =c Ttk 6e3Twhere C is the cement content,k 5,and k 6are constants depend on the materials used.Fig.6shows samples of general mix design nomograph.The nomograph can be used to determine the concrete mix proportion (a)for a given compressive strength but different workability (slump)requirements (Fig.7a)or (b)for a given workability but different strength requirements (Fig.7b).As shown in Fig.6a,according to the required compressive strength f 0c ;1;2;3,one can determined the w/c for concrete mixtures (w/c1,2,3)throughTable 4Compressive strength,lead content and lead-leachability of concrete mixtures.f 0c ;3(MPa)f 0c ;7(MPa)f 0c ;28(MPa)TCLP pH TCLP Pb (mg/L)Total Pb(g/Kg)124.730.035.211.050.4219.6216.720.926.611.430.3216.1318.022.025.911.160.3016.0412.615.820.610.610.3217.158.211.514.011.270.2716.06 6.610.012.611.360.4916.07 5.67.310.310.780.0621.48 5.68.812.010.690.0520.69 4.5 6.59.110.410.3817.31031.535.846.011.011.168.371121.126.334.211.412.1910.41219.325.032.611.190.499.11313.718.523.511.070.359.0149.412.816.111.33 1.088.515 6.49.311.910.871.210.78168.310.514.610.850.2510.1117 5.37.410.011.25 1.2710.76182.93.9 5.610.89 1.110.821922.326.032.810.910.758.872018.625.430.310.961.168.02115.318.227.411.23 1.097.6228.113.419.610.220.277.623 6.210.913.810.60.948.6824 4.88.915.510.570.447.5250.07.29.58.042.419.67260.0 4.37.69.68 1.369.99270.0 2.5 5.49.79 1.189.172828.433.338.0110.834.192922.331.340.911.150.16 4.43015.019.826.410.980.765.23113.816.728.211.460.95 5.03212.015.923.810.40.63 5.513311.712.218.59.750.58 4.19347.413.117.07.33 6.14 6.30357.710.516.38.86 1.436.2436 3.8 6.87.9 6.4133 5.513719.623.825.910.290.227.943816.717.921.810.40.328.93911.212.013.310.540.3711.14026.428.730.2 5.7891.94.7Fig.5.TCLP pH value and Pb content of concrete mixes studied.J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxx5Abram’s Law.Then,the a/c ratio (a/c 1,2,3)can be evaluated through Lyse’s Law based on the w/c and required workability (slump)le-vel.Finally,the cement content (C 1,2,3)can be determined based on the Molinari’s Law from a/c.The concrete mix design is there-fore determined based on these three parameters:w/c,a/c,and C.In order to comply a set of mix design nomograph,a series of mixes with different proportion components (w/c,a/c and C)gen-erally need to be prepared based on controlled workability.The6J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxxperformance (such as compressive strength)of these mixtures are then evaluated and incorporated into the nomograph so as to establish the relation between mix proportion parameters (w/c,a/c and C).Fig.8provides four examples of nomographs of concrete made with different masonry materials and different types of cement.In these nomographs,compressive strength at three different ages (3,7,and 28days)was considered as the concrete performance crite-ria in addition to workability.These nomographs demonstrate sim-ilar trends to those published in the literature [14].Similar nomographs can also be developed if other performance test re-sults,such as ?exural strength,are used to replace concrete strength values in the ?gure.Thus,concrete can be designed to meet the other performance criteria.More nomographs resulting from the present study can be found in the reference reported by Wang et al.[8].The mix design nomographs developed in this study can help ?eld engineers select the proper mix proportion parameters to meet speci?ed concrete performance criteria.Concretes with desir-able compressive strengths and workability levels can be designed using LBP-contaminated recycled aggregates.While these con-cretes might have high concentrations of total lead (up to 2.2%in this study),they would not have a toxicity characteristic for lead and would not be classi?ed as hazardous materials under RCRA.J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxx 75.ConclusionsA variety of concrete mixes was made with four different aggre-gates recycled from lead-contaminated masonry materials,three different kinds of cement,three different aggregate-to-cement ra-tios,and a wide range of water-to-cement ratios.The concrete workability,compressive strength,total lead and lead leachability of the concrete mixes were evaluated.Based on the test results,mix design nomographs were developed.The following conclu-sions can be made: 1.Lead in the LBP-contaminated masonry materials can be sequestered in concrete due to the high alkalinity of cement.Although some masonry materials were classi?ed as hazard materials due to leachable lead content,concrete mixes made with such materials showed no toxicity characteristic for lead according to the Resource Conservation and Recovery Act (RCRA).2.Although having low speci?c gravity and high absorption,crushed masonry materials,without sieving and re-grading process,can be simply used to replace all natural aggregate8J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxxand to produce new concrete that meets structural and con-structability requirements.3.Using of Calcium Sulfoaluminate (CSA)cement signi?cantly increased concrete strength at early ages but had a little effect on the 28-day compressive strength.The CSA cement was less alkaline than Portland cement,and the concrete made with CSA cement had lower pH values than the corresponding con-crete made with Portland cement,thus being less effective for sequestering lead in the concrete.4.Theoretically,phosphate cold react with lead to form hydrox-ypyromorphite,thus resulting in sequestration of lead.How-ever,such a reaction did not occur in the present study and the addition of 5%phosphate had no signi?cant effect on appar-ent total lead content,lead leachability,or compressive strength.5.When well designed and well processed,the concrete made with all recycled aggregate from deconstructed masonry mate-rials can have a large range of workability and strength,thus applicable to various new concrete constructions,such as foun-dation and pavement,reinforcedbeams,columns,and walls.6.The mix design nomograph developed in this study can be used to decide concrete mix design with desired strengths and work-ability.This method can be easily adapted by ?eld engineers for designing concrete with aggregates recycled from different ?eld deconstruction projects. AcknowledgementsThe authors gratefully acknowledge the Strategic Environmen-tal Research and Development Program (SERDP)for sponsor the re-search project and the support provided by the National Concrete Pavement Technology Center (CP Tech Center).Special thanks are given to Mr.Robert Steffes,Dr.David White,Dr.Zhi Ge,and Mr.Eric Lindquist for their assistance in the lab and Mr.John Lathum at the Department of Environmental Health and Safety,Iowa StateUniversity for providing advice and assistance in dealing with occupational safety and hazardous waste issues associated with this project.Mr.Row Carr and Mr.Steve Otto at the Holcim Ltd.kindly provided donations of masonry materials and cement.References[1]ESTCP (Environmental Security Technology Certi?cation Program).ThermalSpray Removal of Lead-Containing Paint of Steel Structures,US Department of Defense,Cost and Performance Report (CP-9607);1999.[2]Hock VF,Edwards-Daniels A.Field demonstration of lead-based paint removaland inorganic stabilization technologies.Environmental Quality Management Inc.;2001.[3]Jacobs DE,Mielke H,Pavur N.The high cost of improper removal of lead-basedpaint from housing:a case report.Environmental Health Perspectives;2003.p.111.[4]Garrels RM,Christ CK,Solutions,minerals,and equilibria.Harper and Row;1965.[5]Brookins DG.Eh–pH diagrams for geochemistry.Springer-Verlag;1988.[6]Cao X,Ma LQ,Chen M,Hardison DW,Harris WG.Weathering of lead bulletsand their environmental effects at outdoor shooting ranges.J Environ Quality 2003;32:526–634.[7]ASTM (American Society for Testing and Materials).Annual Book of ASTMStandards;2010.[8]Wang K,Gaunt JA,Hu J.Sequestering lead in paint by utilizing deconstructedmasonry materials as recycled aggregate in concrete,Strategic Environmental Research and Development Program (SERDP)Project SI 1548;2008.[9]US EPA.Method 1311Toxicity Characteristic Leaching Procedure,CD-ROM,Revision 0;1992.[10]California Code of Regulations.California State of Waste Extraction Test (WET)procedures.California Code of Regulations,Title 22,Division 4.5,Chapter 11,Appendix II;2005.[11]Kosmatka SH,Kerkhoff B,Panarese WC.Design and control of concretemixture.14th ed.Portland Cement Association;2002.[12]Neville AM.Properties of concrete.4th ed.ELBS and Longman;1996.[13]Hu J,Wang K,Gaunt JA.Sequestering lead by utilizing lead based paintcontaminated masonry materials as recycled aggregate in concrete.Resour,Conserv Recy 2010;54(12):1453–60.[14]Levy SM,Helen P.Durability of recycled aggregates concrete:a safe way tosustainable development.Cem Concr Res 2004;34:1975–80.[15]Monteiro PJM,Helene PRL,Kang SH.Designing concrete mixtures for strength,elastic modulus and fracture energy.Mater Struct/Materiaux et Construc 1993;26:443–52.J.Hu et al./Construction and Building Materials xxx (2012)xxx–xxx9。
花生壳论文:花生壳中木犀草素的提取分离

花⽣壳论⽂:花⽣壳中⽊犀草素的提取分离花⽣壳论⽂:花⽣壳中⽊犀草素的提取分离【中⽂摘要】花⽣壳中除含有碳⽔化合物和粗纤维物质外,还含有多种黄酮类化合物。
⽊犀草素是其中主要的黄酮类物质,具有抗菌消炎、解痉祛痰、抗氧化、抗肿瘤等多种药理活性。
花⽣壳是⼀种价廉且可再⽣的天然资源,如能提取并分离其中的有效成分⽊犀草素,将该产物⽤于药物或保健⾷品⽣产,具有⼴阔的市场应⽤前景。
本⽂就酶预处理-醇提联合⼯艺,探讨了酶解液pH值、酶解温度、酶解时间、酶⽤量对花⽣壳中黄酮成分⽊犀草素提取效果的影响。
实验结果显⽰,最优酶预处理提取⼯艺条件为:pH值5.4、酶解温度50℃、酶解时间1.5 h、酶⽤量0.10%。
在该最优预处理条件下,⽊犀草素的提取得率达到2.83 mg·g-1。
同时本⽂依据Fick第⼆定律,对醇溶液提取过程建⽴了提取动⼒学模型。
通过实验测得的⽊犀草素提取得率随提取时间变化的数据,推算出速率常数(k)、活化能(Ea)及有效扩散系数(D)等动⼒学参数值,为⽊犀草素的提取⼯艺设计和操作条件的优化提供了⼀定的理论依据。
利⽤柱层析分离纯化技术,研究了聚酰胺树脂对花⽣壳中⽊犀草素静态吸附的热⼒学和动⼒学特征。
实验测得的吸附等温线符合Langmuir吸附等温式,并利⽤热⼒学函数关系式计算得到吸附焓(ΔH)、⾃由能(ΔG)及吸附熵(ΔS),结果表明该吸附过程是⾃发进⾏且伴随放热的物理吸附过程。
同时采⽤拟⼀级反应和拟⼆级反应模型描述了吸附动⼒学数据,得出拟⼆级吸附动⼒学模型能更好地描述聚酰胺树脂对⽊犀草素的吸附⾏为。
另外,通过动态吸附实验测定了穿透曲线,得到聚酰胺树脂对⽊犀草素的动态吸附容量(Q)为0.2817 mg·g-1,总传质系数(KFav)为0.0570 s-1,传质长度(Za)为28.40 cm,为⽊犀草素⽣产的放⼤操作提供了实验和理论依据。
经不同⽐例的醇溶液梯度洗脱分离花⽣壳提取液中的⽊犀草素,确定75%⼄醇溶液洗脱效果最佳。
二氯二氢硅反歧化反应精馏工艺的模拟分析与控制
运行参数对比如表1所示,温度、压力及各组分的误 差均不超过5%。工业数据和模拟数据存在差异的原 因主要有以下两方面:一方面是由于工业上根据控
制结构调控反应精馏塔时存在时间差异,该塔并不
是时刻处于质量守恒的状态;另一方面由于工业中
催化剂活性降低和气液固三相接触导致实际的反
应转化率和分离效率与模拟数据存在一定的差异。
LI Chen-chen1,2, LU Ping*, CAO Jun-ya!, HUA Chao2,3, BAI Fang2,3
(1. School of Chemistry and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China; 2. Key Laboratory of Green Process Engineering, Institute of Process Engineering, Chinese Academy of Science, Beijing
陆平(1980-),副研究员,硕士生导师,研究方向为高效精馏与提纯,电话:18501289940,E-mail:ipepinglu@。
第3期
李晨晨等:二氯二氢硅反歧化反应精馏工艺的模拟分析与控制
89
行业的发展有着重要的意义。截至目前,主要通过 还原法叫反应沉积法化反歧化 [5]等方法实现DCS的 回收利用,其中反歧化法是将DCS和STC在催化剂 的作用下反应生成TCS (见反应式⑴),实现了改良 西门子法中DCS回收利用的循环闭路,成为目前处 理DCS的主要手段。
SiH2Cl2 + SiCl4 <==>2SiHCl3
对苯二甲酸锌
对苯⼆甲酸锌Hydrothermal Synthesis and Crystal Structure of a Novel 2-Fold Interpenetrated Framework Based on Tetranuclear Homometallic ClusterRong-Yi Huang ?Xue-Jun Kong ?Guang-Xiang LiuReceived:15December 2007/Accepted:11January 2008/Published online:5March 2008óSpringer Science+Business Media,LLC 2008Abstract A novel 2-fold parallel interpenetrated polymer,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1)(pheno =phenan-threne-9,10-dione;p -BDC =1,4-benzenedicarboxylate)was prepared by hydrothermal synthesis and characterized by IRspectra,elemental analysis and single crystal X-ray /doc/c97a12ccf61fb7360b4c65f3.html plex1crystallizes in the orthorhombic space group Pbca and affords a three-dimensional (3D)six-connected a -Ponetwork.Keywords Carboxylate ligand áHomometallic complex áa -Po1IntroductionIn the last decade,the construction by design of metal-organic frameworks (MOFs)using various secondary building units (SBUs)connected through coordination bonds,supramolecular contacts (e.g.,hydrogen bonding,p áááp stacking,etc.),or their combination has been an increasingly active research area [1].The design and controlled assembly of coordination polymers based on nano-sized MO(OH)clusters and multi-functional car-boxylates have been extensively developed for their crystallographic and potential applications in catalysis,nonlinear optics,ion exchange,gas storage,magnetism and molecular recognition [2].In most cases,multinu-clear metal cluster SBUs can direct the formation of novel geometry and topology of molecular architectureand help to retain the rigidity of the networks [3].A number of carboxylate-bridged metal clusters have been utilized to build extended coordination frameworks.Among these compounds,frameworks from multinuclear zinc cluster SBUs,including dinuclear (Zn 2)[4],trinu-clear (Zn 3)[5],tetranuclear (Zn 4)[6],pentanuclear (Zn 5)[7],hexanuclear (Zn 6)[8],heptanuclear (Zn 7) [9],and octanuclear (Zn 8)[10]clusters have attracted great interest and have been investigated extensively.Addi-tionally,a series of systematic studies on this subject has demonstrated that an interpenetrated array cannot prevent porosity,but enhances the porous functionalities of the supramolecular frameworks [11].More importantly,the research upsurge in interpenetration structures was pro-moted by the fact that interpenetrated nets have been considered as potential super-hard materials [12]and possess peculiar optical and electrical properties [13].Herein we present the synthesis,structure,and spectral properties of a new coordination polymer based on tetranuclear homometallic cluster,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1).2Experimental2.1Materials and MeasurementsAll commercially available chemicals are reagent grade and used as received without further puri?cation.Sol-vents were puri?ed by standard methods prior to use.Elemental analysis for C,H and N were carried with a Perkin-Elmer 240C Elemental Analyzer at the Analysis Center of Nanjing University.Infrared spectra were obtained with a Bruker FS66V FT IR Spectrophotometer as a KBr pellet.R.-Y.Huang áX.-J.Kong áG.-X.Liu (&)Anhui Key Laboratory of Functional Coordination Compounds,College of Chemistry and Chemical Engineering,Anqing Normal University,Anqing 246003,P.R.China e-mail:liugx@/doc/c97a12ccf61fb7360b4c65f3.htmlJ Inorg Organomet Polym (2008)18:304–308DOI 10.1007/s10904-008-9199-72.2Preparation of Zn2(OH)(pheno)(p-BDC)1.5áH2O(1)A mixture containing Zn(NO3)2á6H2O(0.20mmol), p-1,4-benzenedicarboxylic acid(H2BDC)(0.20mmol), phenanthrene-9,10-dione(pheno)(0.10mmol)and NaOH (0.20mmol)in water(10mL)was sealed in a18mL Te?on lined stainless steel container and heated at150°C for72h.The reaction product was dark yellow block crystals of1,which were washed by deionized water sev-eral times and collected by?ltration;Yield,78%. Elemental Analysis:Calcd.for C24H15N2O10Zn2:C,46.33;H,2.43;N,4.50%.Found:C,46.38;H,2.47;N,4.48%.IR (KBr pellet),cm-1(intensity):3437(br),3062(m),1587(s),1523(m),1491(w),1424(m),1391(s),1226(w),1147 (w),1103(w),1051(w),875(w),843(m),740(w),728 (m),657(w).2.3X-ray Structure DeterminationThe crystallographic data collections for complex1were carried out on a Bruker Smart Apex II CCD with graphite-monochromated Mo-K a radiation(k=0.71073A?)at 293(2)K using the x-scan technique.The data were inte-grated by using the SAINT program[14],which also did the intensities corrected for Lorentz and polarization effects.An empirical absorption correction was applied using the SADABS program[15].The structures were solved by direct methods using the SHELXS-97program; and,all non-hydrogen atoms were re?ned anisotropically on F2by the full-matrix least-squares technique using the SHELXL-97crystallographic software package[16,17]. The hydrogen atoms were generated geometrically.All calculations were performed on a personal computer with the SHELXL-97crystallographic software package[17].The details of the crystal parameters,data collection and re?nement for four compounds are summarized in Table1. Selected bond lengths and bong angles for complex1are listed in Table2.3Results and DiscussionThe X-ray diffraction study for1reveals that the material crystallizes in the orthorhombic space group Pbca and features a2-fold parallel interpenetrated3D?3D net-work motif.The asymmetric unit contains two Zn(II) atoms,one hydroxyl,one pheno ligand,one and half of p-BDC molecules and one solvent water molecule.Selected bond lengths for1are listed in Table2.As shown in Fig.1, the Zn1ion,which is in the center of a tetrahedral geom-etry,is surrounded by three carboxylic oxygen atoms (Zn–O=1.918(5)–1.964(5)A?)from three p-BDC ligands and one l3-OH oxygen atom(O9).The Zn–O distance is1.965(5)A?.Two nitrogen atoms(N1and N2)that belong to pheno,one p-BDC oxygen atom(O3A)and one hydroxyl oxygen atom(O9A)are ligated to the Zn2center in the equatorial plane with another oxygen atom(O9)that arises from the second hydroxyl group and one oxygen atom(O5)that arises from the second p-BDC molecule situated in the axial position.EachZn2lies approximately in the equatorial position with a maximum deviation (0.048A?)from the basal plane.In the structure,Zn–O and Zn–N bond distances are in the range of 2.0530(5)–2.112(5)and2.157(5)–2.184(2)A?,respectively. There exist two types of p-BDC found in1(Scheme1); namely,monobidentate bridging(l3)and bi-bidentatebridging(l4)coordination modes.The bidentate bridging p-BDC connects mixed metals,where the smallest ZnáááZn distance is3.163A?,to complete a homodinuclear cluster, which is further linked by l3-OH into a six-connected Table1Crystal data and summary of X-ray data collection for1Zn2(pheno)(OH)(BDC)1.5áH2O Empirical formula C24H15N2O10Zn2Molecular mass/g mol-1622.12Color of crystal Dark yellowCrystal fdimensions/mm0.1890.1690.12 Temperature/K293Lattice dimensionsa/A?18.777(9)b/A?13.657(6)c/A?19.983(9)a/°90b/°90c/°90Unit cell volume(A?3)5125(4)Crystal system OrthorhombicSpace group PbcaZ8l(Mo-K a)/mm-1 1.931D(cacl.)/g cm-3 1.613Radiation type Mo-K aF(000)2504Limits of data collection/° 2.04B h B25.05Total re?ections24155Unique re?ections,parameters4545,347No.with I[2r(I)2821R1indices[I[2r(I)]0.0657w R2indices0.1858Goodness of?t 1.060Min/max peak(Final diff.map)/e A?-3-0.658/2.322tetranuclear cluster that is jointly coordinated by six p-BDC molecules(Fig.2).The clusters are further extended by p-BDC into a single3D framework(Fig.3).For clarity, we used the topological method to analyze this3D framework.Thus,the six-connected SBU is viewed to be a six-connected node.Furthermore,based on consideration of the geometry of thisnode,the3D frame is classi?ed as an a-Po net with41263topology(Fig.4).Of particular interest,the most intriguing feature of complex1is that a pair of identical3D single nets is interlocked with each other,thus directly leading to the formation of a2-fold interpenetrated3D?3D architecture(Fig.4)and the two pcu(a-Po)frameworks are related by a screw axis21[18]. Recently,a complete analysis of3D coordination networks shows that more than50interpenetrated pcu(a-Po)frames have been documented in the CSD database[18],including 2-fold,3-fold[19],and4-fold[20]interpenetration.In addition,several non-interpenetration motifs with a-Po topology have been reported to date[21].ZnZnO ZnZnZnZnO Znbidentate bidentate bidentate monodentateI IIScheme1Coordination modesof the bdc ligands in the structure of1;I is bis(bidentate),II is bi/monodentateFig.1ORTEP representation of complex1(the H atoms have been omitted for the sake of clarity).The thermal ellipsoids are drawn at 30%probabilityTable2Selected bond lengths(A?)and angles(°)for1Symmetry transformations usedto generate equivalent atoms:#1x-1/2,y,-z+1/2;#2-x,-y+1,-z;#3-x+1/2,-y+1,z-1/2Zn(1)–O(1) 1.918(5)Zn(2)–O(9)#2 2.091(4)Zn(1)–O(4)#1 1.953(5)Zn(2)–O(9) 2.103(5)Zn(1)–O(6) 1.964(5)Zn(2)–O(3)#3 2.112(5)Zn(1)–O(9) 1.965(5)Zn(2)–N(1) 2.157(6)Zn(2)–O(5)#2 2.053(5)Zn(2)–N(2) 2.184(6)O(1)–Zn(1)–O(4)#197.9(2)O(9)–Zn(2)–O(3)#388.81(18)O(1)–Zn(1)–O(6)112.9(2)O(5)#2–Zn(2)–N(1)94.7(2)O(4)#1–Zn(1)–O(6)104.7(2)O(9)#2–Zn(2)–N(1)170.7(2)O(1)–Zn(1)–O(9)122.9(2)O(9)–Zn(2)–N(1)91.6(2)O(4)#1–Zn(1)–O(9)109.7(2)O(3)#3–Zn(2)–N(1)88.9(2)O(6)–Zn(1)–O(9)107.0(2)O(5)#2–Zn(2)–N(2)87.1(2)O(5)#2–Zn(2)–O(9)#291.9(2)O(9)#2–Zn(2)–N(2)98.3(2)O(5)#2–Zn(2)–O(9)173.72(19)O(9)–Zn(2)–N(2)94.5(2)O(9)#2–Zn(2)–O(9)81.82(19)O(3)#3–Zn(2)–N(2)164.3(2)O(5)#2–Zn(2)–O(3)#391.3(2)N(1)–Zn(2)–N(2)75.7(2)O(9)#2–Zn(2)–O(3)#397.42(19)Fig.2Polyhedral representation of the homotetranuclear unit as asix-connected node linked by p-BDC ligandsMoreover,rich inter and intra hydrogen-bonds between the water molecules and the carboxylate groups (Table 3)further strengthen the stacking of the supra-architecture (Fig.5).4Supplementary MaterialsCrystallographic data (excluding structure factors)for thestructures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supple-mentary publication /doc/c97a12ccf61fb7360b4c65f3.html DC-666555.Copies of the data can be obtained free of charge on application to CCDC,12Union Road,Cambridge CB21EZ,UK (Fax:+44-1223-336033;e-mail:deposit@/doc/c97a12ccf61fb7360b4c65f3.html ).Acknowledgments This work was supported by the National Nat-ural Science Foundation of China (20731004)and the Natural Science Foundation of the Education Committee of Anhui Province,China(KJ2008B004).Fig.3Polyhedral presentation of one set of the 3D network along a -axis (a )and b -axis (b )Table 3Distance (A ?)and angles (°)of hydrogen bonding for com-plex 1D–H áááADistance of D áááA (A ?)Angle of D–H–A (°)O1W–H1WB áááO2#1 2.677(9)164O9–H19áááO1W#2 2.841(9)151C13–H13áááO3#3 3.045(10)121C22–H22áááO1W#43.353(10)167Symmetry transformations used to generate equivalent atoms:#1x,y,1+z;#2-x,1-y,-1+z;#3-x+1/2,-y+1,z -1/2;#4-x,1-y,1-zFig.4Simpli?ed schematic representation of the 3D ?3D two-fold interpenetrated a -Po network in1Fig.5Projection of the structure of 1along b -axis (dotted lines represent hydrogen-bonding)References1.(a)P.J.Hagrman,D.Hagrman,J.Zubieta,Angew.Chem.Int.Ed.38,2638(1998);(b)S.Leininger,B.Olenyuk,P.J.Stang,Chem.Rev.100,853(2000);(c)A.Erxleben,Coord.Chem.Rev.246, 203(2003);(d)K.Biradha,Y.Hongo,M.Fujita,Angew.Chem. 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美国密执安州大学研制出基于碳纳米管的非低温制冷红外传感器
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油井化学堵水效果评价方法及应用
技术应用/TechnologyApplication油井化学堵水效果评价方法及应用付亚荣刘泽姜春磊翟中杨杨亚娟吴泽美季保汐敬小龙唐光亮(中国石油华北油田公司)摘要:我国油田堵水调剖技术已经历60多年的发展历程,油井堵水、注水井调剖、调驱以及深部液流转向等技术经历了起源、试验、发展、成熟、更替的过程,取得了很好的增油效果。
大多学者重点关注堵水技术和方法的研究,堵水效果如何评估研究较少。
为此,将油井化学堵水波及油层分为内、外两区域,增加的原油产量在达西渗流线性系统中理论上无限叠加,以内区、外区、交界面等3个产出液流动控制方程为理论依据,基于Duhamdl 原理的反褶积算法,建立油井井口压力模型、有效渗透率模型、产油量计算模型等评价油井化学堵水效果。
在50多口油井应用后,评价符合率达到95%以上,消除了技术人员习惯直接利用堵水前后产油量的差值判断堵水效果所带来的不确定性,为油井化学堵水效果评价提供了一种新的方法。
关键词:油井;高含水;化学堵水;反褶积算法;评价符合率DOI :10.3969/j.issn.2095-1493.2024.03.001Evaluation method and application of chemical plugging effect in oil wellsFU Yarong,LIU Ze,JIANG Chunlei,ZHAI Zhongyang,YANG Yajuan,WU Zemei,JI Baoxi,JING Xiaolong,TANG Guangliang North China Oilfield Company,CNPCAbstract:China's oilfield water plugging and profile control technology has experienced more than 60years of development.The water plugging in oil wells,profile control in water injection wells,profile control and flooding,as well as deep fluid flow diversion and other technologies have gone through the process of origin,test,development,maturity and replacement,which achieved good oil increase effect.Most scholars mainly focus on the research of water plugging technology and methods,but there are few research on how to evaluate the water plugging effect.Hence,the oil well chemical water plugging wave and oil layer are divided into internal and external areas.The Darcy percolation linear system that was increased crude oil production is infinitely superposed in theory,and the three pro-duced fluid flow control equations of the inner zone,the outer zone and the interface are taken as the theoretical basis.Based on the anti-convolution algorithm of Duhamd l principle,the well head pres-sure model,effective permeability model and oil production calculation model are established to evalu-ate the effect of oil well chemical water plugging.After the application of more than 50oil wells,the coincidence rate of evaluation is more than 95%,which eliminates the uncertainty caused by technical personnel that are accustomed to directly judging the water plugging effect through using the difference in oil production before and after water plugging and provides a new method for evaluating the chemi-cal water plugging effect of oil wells.Keywords:oil well;high water content;chemical plugging;anti-convolution algorithm;coinci-dence rate of evaluation第一作者简介:付亚荣,教授级高级工程师,1987年毕业于重庆石油学校(油田应用化学专业),从事油气田开发技术研究与应用工作,引文:付亚荣,刘泽,姜春磊,等.油井化学堵水效果评价方法及应用[J].石油石化节能与计量,2024,14(3):1-5.FU Yarong,LIU Ze,JIANG Chunlei,et al.Evaluation method and application of chemical plugging effect in oil wells[J].Energy Conservation and Measurement in Petroleum &Petrochemical Industry,2024,14(3):1-5.付亚荣等:油井化学堵水效果评价方法及应用第14卷第3期(2024-03)陆相水驱开发油藏油层内部纵向非均质严重,油井出水是普通存在的问题。
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Journal of Process Control 22 (2012) 1182–1197Contents lists available at SciVerse ScienceDirectJournal of ProcessControlj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /j p r o c o ntDynamics and control of totally refluxed reactive distillation columnsWei Liu a ,Kejin Huang a ,∗,Liang Zhang a ,Haisheng Chen a ,San-Jang Wang ba College of Information Science and Technology,Beijing University of Chemical Technology,Beijing 100029,People’s Republic of China bDepartment of Chemical and Material Engineering,Ta Hwa Institute of Technology,Chiunglin,Hsinchu 307,Taiwana r t i c l ei n f oArticle history:Received 3August 2011Received in revised form 3May 2012Accepted 10May 2012Available online 15 June 2012Keywords:Reactive distillation column Totally refluxed operation Process dynamics Inventory control Process operationa b s t r a c tAccording to the mechanism of the reaction operation involved,reactive distillation columns are often designed to work in a totally refluxed operation mode.The totally refluxed operation mode makes the reflux drum interact solely with the reaction operation involved and retards considerably the dynamics of the latter.The resultant great difference in process dynamics between the reaction operation and the separation operation involved leads frequently to under-damped responses with the degree of under-dampness closely dependent on the inventory control of the reflux drum.With the tight inventory control of the reflux drum,the degree of under-dampness can be suppressed and this presents a favorable effect to process dynamics and controllability of the totally refluxed reactive distillation columns.Two hypothet-ical ideal reactive distillation columns with and without a side reaction,respectively,and a high-purity ethylene glycol reactive distillation column are employed to examine the unique dynamics and control-lability of the totally refluxed reactive distillation columns.The results obtained are in good accordance with the above interpretation.The current work reveals the general behaviors of the totally refluxed reactive distillation columns and can be particularly useful in control system synthesis and design.© 2012 Elsevier Ltd. All rights reserved.1.IntroductionAccording to the mechanism of the reaction operation involved,reactive distillation columns are often designed to work in a totally refluxed operation mode.For example,in case of carrying out a reaction,A +B ↔C,in a reactive distillation column,the desired product C should be withdrawn from the bottom of the process because it is the heaviest component.At the top of the reactive dis-tillation column,the reactants,A and B,are usually accumulated and they should be recycled back to the reactive section through a totally refluxed operation mode in reflux drum.Since there is no rectifying section in the reactive distillation column,the reflux drum is directly connected to the reactive section and this leads to an intimate interaction between them.Such interaction affects considerably the reaction operation involved and can eventually present a strong impact to the dynamics and controllability of the totally refluxed reactive distillation columns.These should repre-sent the unique behaviors of the totally refluxed reactive distillation columns and are worthwhile to be studied carefully.Recent years have seen increasingly more studies conducted on the dynamics and operation of reactive distillation columns [1–6].For the totally refluxed reactive distillation columns,there have also appeared a number of papers dealing with their operation∗Corresponding author.Tel.:+861064434801;fax:+861064437805.E-mail address:huangkj@ (K.Huang).issues.Luyben once compared the operation of two ternary ideal reactive distillation columns with and without chemically inert components,respectively [7].He found that the presence of a chemically inert component could alter the process from a totally refluxed operation mode into a partially refluxed operation mode.In particular,a direct measurement of stage composition is required for the effective process control.Recently,Kaymak et al.fur-ther explored the inferential temperature control of the ternary ideal reactive distillation columns with and without chemically inert components [8,9].They insisted that the direct measure-ment of stage composition might not be necessary provided that the control structure and control tray locations were properly chosen.Ethylene glycol reactive distillation column represents a typical example for the totally refluxed reactive distillation col-umn and has received considerable attention in the aspects of process dynamics and controllability.Although Kumar and Daou-tidis claimed that nonlinear controller was superior to linear PI controller in its operation [10],Al-Arfaj and Luyben showed that the process could be effectively controlled by a simple PI con-trol scheme plus a feed-forward compensator [11].Huang et al.addressed internal heat integration to a high-purity ethylene gly-col reactive distillation column [12,13].They found that seeking further internal heat integration between the reaction operation and the separation operation involved helped to improve the process dynamics and lessened the difficulties in process opera-tion.Furthermore,the tight inventory control of the reflux drum could function to suppress the inherent process nonlinearity and0959-1524/$–see front matter © 2012 Elsevier Ltd. All rights reserved./10.1016/j.jprocont.2012.05.007W.Liu et al./Journal of Process Control22 (2012) 1182–11971183NomenclatureA hypothetical componentA vp vapor pressure constant(Pa)B hypothetical componentBot bottom productflow rate(mol s−1)B vp vapor pressure constant(Pa K)C hypothetical componentCC composition controllerD hypothetical componentDEG diethylene glycolE activation energy of reaction(J mol−1)EG ethylene glycolEO ethylene oxideF feedflow rate(mol s−1)FCflow controllerH stage holdup(mol)H R heat of reaction(J mol−1)H V latent heat of vaporization(J mol−1)k controller gaink con controller gain of reflux drum level(s−1)L liquidflow rate(mol s−1)LC level controllernc total number of componentsNT total number of stagesPC pressure controllerR ideal gas law constant(J mol−1K−1)r reaction rate(mol mol−1s−1or mol m−3s−1)T temperature(K)T i reset time(s)V vaporflow rate(mol s−1)W waterx liquid compositionz feed compositionGreek symbols˛pre-exponential factorstoichiometric coefficient of a reactionSubscriptsb backward reactionf forward reactioni component indexj stage indexm main reactions side reactionnon-minimum phase behavior,favoring therefore process oper-ation significantly.Although this conclusion was acquired from the high-purity ethylene glycol reactive distillation column,it invoked us to anticipate that the interesting phenomenon might be closely related to the particular structure of the totally refluxed reactive distillation columns.This consideration stimulated us to acquire the insights of the phenomenon.To the best of our knowl-edge,until now no pertinent work has been conducted on the relationship between process configuration and process dynam-ics and controllability for the totally refluxed reactive distillation columns.The primary objective of the current work is to investigate the dynamics and control of the totally refluxed reactive dis-tillation columns.Two hypothetical ideal reactive distillation columns with and without a side reaction,respectively,and a high-purity ethylene glycol reactive distillation column are cho-sen as representative examples.Both open-loop process dynamics and closed-loop operation are examined with special atten-tion focused on the effect of inventory control of reflux drum. The unique behaviors of the totally refluxed reactive distillation columns are analyzed and the acquired insights are then summa-rized.2.Unique process dynamics and its implications on the control of the totally refluxed reactive distillation columns Unlike the conventional reactive distillation columns with distillate and bottom withdrawal,the totally refluxed reactive distillation columns contain a reactive section with a direct con-nection to the reflux drum(because there is no rectifying section). In an extreme point of view,it is even reasonable to treat them as an equivalent reactor with heat exchange in the condenser. Because of the large liquid holdup in the reflux drum,once the light and/or heavy reactants enter the reflux drum,they will gen-erally need a long time to be driven back to the reactive section and this retards considerably the dynamics of the reaction operation involved.In the totally refluxed reactive distillation columns,the sep-aration operation involved is solely carried out in the stripping section.Since the heat duty of reboiler(or the reboilflow rate) serves as the manipulated variable to control the purity of bottom product,it should be taken as the main variable to represent the dynamics of the separation operation involved.Because the bottom reboiler has much faster dynamics than the liquid hydraulics in the reflux drum and in the reactive section compounded further with the reaction kinetics,sharp difference exists in process dynam-ics between the reaction operation and the separation operation involved.This causes generally under-dampness in the open-loop dynamic responses of the bottom product.The greater the differ-ence is,the severer the degree of the under-dampness becomes. Moreover,the sharp difference in process dynamics between the reaction operation and the separation operation involved can also induce a certain degree of degradation in system properties,e.g., in the aspects of process nonlinearity and non-minimum phase behavior.This inevitably gives rise to additional difficulties in pro-cess operation.In terms of the above analysis,one can now understand that the sharp difference in process dynamics between the reaction oper-ation and the separation operation involved is the main reason for the occurrence of the under-damped behaviors in the totally refluxed ideal reactive distillation columns.To suppress the degree of the under-dampness,one must therefore rely on the acceleration of reaction kinetics and liquid hydraulics in the reactive section and in the reflux drum.Although operating pressure can be increased to accelerate reaction kinetics,it is generally determined by the match of operating conditions between the reaction operation and the separation operation involved.For the liquid hydraulics in the reactive section and in the reflux drum,it is decided by process capacity and is usually operationally infeasible to be enhanced through the reduction of their sizes.The only way left is to acceler-ate the dynamics of the reflux drum through tight control of liquid level.Remember,however,that this differs totally from the conven-tional design practice,i.e.,the inventory of the reflux drum should be loosely controlled in order to avoid strong interaction between different control loops.In the remainder of this paper,we will employ three totally refluxed reactive distillation columns,including two hypotheti-cal ideal reactive distillation columns with and without a side reaction,respectively,and a high-purity ethylene glycol reac-tive distillation column,to examine their unique dynamics and the effect of inventory control of reflux drum on process opera-tion.1184W.Liu et al./Journal of Process Control22 (2012) 1182–1197Table1Physicochemical properties and operating conditions of Example I.Parameter Value Column pressure(bar)8.0Number of stages Rectifying section0 Reactive section9 Stripping section5Liquid hodlup(mol)Condenser20,000.0 Column tray1000.0 Reboiler20,000.0Reaction activation energy(J mol−1)Forward125,520 Backward125,520Specific reaction rate at366K(mol s−1mol−1)Forward0.008 Backward0.0004Feedflow rate(mol s−1)A12.63 B12.82Feed location A10 B2Feed thermal condition A 1.0B 1.0Relative volatility(A:B:C)4:2:1 Heat of reaction(J mol−1)0Latent heat of vaporization(J mol−1)29,053.7 Bottom product specification(C,mol%)98Vapor pressure constants A(A vp/B vp)12.3463/3862 B(A vp/B vp)11.6531/3862 C(A vp/B vp)10.9600/38623.Example I:A totally refluxed ideal reactive distillation system involving one reaction with two light reactants and one heavy product3.1.Process descriptionThis hypothetical ideal reactive distillation system is taken from Sun et al.[14].As is shown in Fig.1,this reactive distillation column consists of a reactive section above the stripping section with9and 5stages,respectively.The reactive distillation column is operated in a totally refluxed operation mode,and two pure reactant feeds,F A and F B,are fed to stages10and2(numbered from the top condenserCFig.1.Scheme of a totally refluxed ideal reactive distillation column with one reac-tion(Example I).down to the bottom reboiler,and similarly hereinafter),respec-tively,with the latter in slight excess.Detailed physicochemical properties and operating conditions are listed in Table1,and other relevant information can be found in the corresponding reference.In the reactive section of this totally refluxed ideal reactive distil-lation column,reactants A and B undergo a reversible liquid-phase reaction to form the desired product C.The detailed reaction mech-anism isA+B↔C(1) The volatilities are such that the product C is the heavy key,A is the light key,and B is the intermediate key.The net reaction rate for component i on reactive stage j is given byr i,j= i H j(K f,j x A,j x B,j−K b,j x C,j)(2) where K f,j and K b,j are the forward and backward specific reaction rate constants,respectively,described by the Arrhenius law asK f,j=˛f exp−E fRT j(3.1) K b,j=˛b exp−E bj(3.2)Equimolar overflow is assumed in the nonreactive section.As the reaction reduces the molecular number,i.e.,nci=1i=−1(4) the mass balance equations in the reactive section becomeV j=V j+1−r j H RV(5) L j=L j−1+nci=1r i,j+r j H RH V(6)Ideal vapor and liquid phase behaviors are assumed in the vapor–liquid equilibrium calculation.The steady-state profiles of temperature,vapor and liquidflow rates,liquid composition,and net reaction rates are calculated and shown in Fig.2.W.Liu et al./Journal of Process Control 22 (2012) 1182–11971185370390410430450abcd161310741T (K )Stage nu mber0204060161310741L & V F l o w r a t e (m o l ·s –1)Stage nu mberLV0.00.2 0.4 0.6 0.8 1.0 161310741x (m o l e f r a c t i o n )Stage numberABC12345161310741R e a c t i o n R a t e (m o l ·s –1)Stage nu mberFig.2.Steady-state profiles of Example I.(a)Temperature,(b)vapor and liquid flow rates,(c)liquid composition and (d)net reaction rates.3.2.Evaluation of open-loop process dynamicsIn Fig.3,the open-loop transient responses of the totallyrefluxed ideal reactive distillation column with different k con (i.e.,k con =0.2,1.0,and 2.5s −1)are depicted,when it is subjected to a ±5%step change in the reboil flow rate,respectively.Sharp differ-ences can be found between the positive and negative responses,irrespective of the detailed parameters assigned to the inventory controller of the reflux drum.In the case of the positive change in the reboil flow rate,the totally refluxed ideal reactive distil-lation column exhibits under-damped responses with the degree of under-dampness inversely proportional to the controller gain of the reflux drum.In the case of the negative change in the reboil flow rate,the totally refluxed ideal reactive distillation column still displays under-damped responses with the degree of under-dampness inversely proportional to the controller gain of the reflux drum and this can clearly be observed before the time instant of 4h.After that time instant,transition between the inherent multiple steady states occurs and this moves the totally refluxed ideal reactive distillation column to an unexpected steady state.This is why a high degree of asymmetry has been noticed between the positive and negative responses in this sit-uation.The open-loop transient responses of the totally refluxed ideal reactive distillation column with different k con are shown in Fig.4,when it is confronted with a ±2%step change in the feed flow rate of reactant B,respectively.No under-damped responses are observed and the variation in the controller gain of the reflux drum shows almost no impact on the system responses.Regard-less of the positive and negative changes in the feed flow rate of reactant B,the composition of the bottom product settles down to two values lower than the initial steady state,imply-ing the possible transition between the inherent multiple steady states.0.97 80.980.9820.98 40.98 60.98 8ab12108642x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.50.930.950.970.99403224168x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.5Fig.3.Open-loop transient responses of the totally refluxed ideal reactive distilla-tion column with different k con in the face of a ±5%step change in the reboil flow rate,respectively (Example I).(a)Positive responses and (b)negative responses.1186W.Liu et al./Journal of Process Control 22 (2012) 1182–1197Table 2Controller parameters for Example I.ParameterControl loopReflux drum levelBase levelStoichiometric balanceBottom Ck0.2/1.0/2.50.211.130.9T i (min)–––0.423.3.Evaluation of closed-loop control performanceClosed-loop control of the totally refluxed ideal reactive distil-lation column is conducted to evaluate the impact of the inventory control of the reflux drum.A control scheme that uses two direct composition control loops is selected in the current study and Fig.5provides the detailed control structure [7].The pressure is assumed to be perfectly controlled at the nominal steady-state by the heat removal of condenser.The level of the reflux drum is controlled by reflux flow rate,and a P-only controller is used.The level of rebolier is controlled by the bottom product flow rate,and a P-only controller is chosen.The composition of the bottom product is controlled by the heat duty of reboiler,and a PI controller is adopted.According to the steady-state com-position profile in Fig.2,the composition of stage 3is selected to be controlled by the feed flow rate of reactant B because it changes rapidly there.This composition loop serves to regulate the stoichiometric balance between the two reactants,and a P-only controller is adopted.The feed flow rate of reactant A is the production rate handle and flow controlled.The composition con-trollers are tuned with Ziegler–Nichols tuning method and all the controller parameters are listed in Table 2.A first-order lag with a time constant of 5-min is inserted in all composition control loops.0.95 50.96 50.97 50.9850 8 16 24 3240x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.50.90.930.960.99816 243240x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.5abFig.4.Open-loop transient responses of the totally refluxed ideal reactive distilla-tion column with different k con in the face of a ±2%step change in the feed flow rate of reactant B,respectively (Example I).(a)Positive responses and (b)negative responses.The composition transmitter spans are set to be 0.1and all thecontrol valves are designed to be half open at the nominal steady state.The servo responses of the totally refluxed ideal reactive distil-lation column are illustrated in Fig.6,when the controller of the bottom product purity is subjected to a ±0.3mol%step change in its set-point,respectively.It is noted that strong effect has been generated by the variation in the controller gain of the reflux drum for both the positive and negative changes in the set-point of the bottom control loop.With increasingly tight inventory control of the reflux drum,the totally refluxed ideal reactive distillation col-umn displays a consistent improvement in dynamic responses in the case of positive change in the set-point of the bottom control loop.In the case of the negative change in the set-point of the bot-tom control loop,sustainable oscillations occur when the controller gain of the reflux drum has been set at 0.2and 1.0s −1respectively.After it has been increased to 2.5s −1,the sustainable oscillation is vanished.Fig.7presents the regulatory responses of the totally refluxed ideal reactive distillation column,when a ±2%step change is introduced to the production rate,respectively,in terms of a corre-sponding variation in the feed flow rate of reactant A.Quite similar to the circumstances of the step changes in product purity for the bottom control loop,the totally refluxed ideal reactive distillation column exhibits improved responses with the increasingly tight inventory control of the reflux drum.More specifically,whereas the low controller gain (i.e.,k con =0.2s −1)of the reflux drum resultsCFig.5.Control scheme of Example I.W.Liu et al./Journal of Process Control 22 (2012) 1182–119711870.97 90.9810.98 30.98 5024681012x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.50.960.970.980.9902468 1012x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.53334353637024681012V [16](m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon= 2.53032.53537.54002468 1012V [16](m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.534353637024681012R e f l u x (m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.532333435363702468 1012R e f l u x (m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.5abFig.6.Servo responses of the totally refluxed ideal reactive distillation column with different k con in the face of a ±0.3mol%step change in the set-point of the bottom composition control loop,respectively (Example I).(a)Positive responses and (b)negative responses.in sustainable and yet magnified oscillations,the high ones (i.e.,k con =1.0or 2.5s −1)achieve a stable operation.4.Example II:A totally refluxed ideal reactive distillation column with one main and one side reactions4.1.Process descriptionThis hypothetical ideal reactive distillation system is developed from Example I with the inclusion of an additional reversible side reactionB +C ↔D(7)As shown in Fig.8,the process configuration is exactly similar to that of Example I (c.f.,Fig.1).The main and side reaction rates for component i on reactive stage j are given byr m i,j = m i H j (K f m ,j x A ,j x B ,j −K b m ,j x C ,j )(8.1)r s i,j = s i H j (K f s ,j x B ,j x C ,j −K b s ,j x D ,j )(8.2)In terms of relative volatilities,these four components can be arranged in the following order:A >B >C >D(9)which means the component D is also withdrawn with component C from the bottom of the totally refluxed ideal reactive distilla-tion column.Detailed physicochemical properties and operating conditions are tabulated in Table 3.The steady-state profiles of tem-perature,vapor and liquid flow rates,liquid composition,and net reaction rates are calculated and shown in Fig.9.4.2.Evaluation of open-loop process dynamicsIn Fig.10,the open-loop transient responses of the totally refluxed ideal reactive distillation column with different k con (i.e.,k con =0.2, 1.0,and 2.5s −1)are depicted,when there is a ±5%step change in the reboil flow rate,respectively.1188W.Liu et al./Journal of Process Control 22 (2012) 1182–11970.97 80.980.98 202468 1012x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon= 2.50.97 80.980.98202468 1012x C (m o l e f r a c t i o n )Time (h)kcon = 0.2kcon = 1.0kcon = 2.53434.53535.53602468 1012V [16](m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon= 2.53333.53434.53502468 1012V [16](m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.53434.53535.502468 1012R e f l u x (m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.533343502468 1012R e f l u x (m o l ·s –1)Time (h)kcon = 0.2kcon = 1.0kcon = 2.5ab Fig.7.Regulatory responses of the totally refluxed ideal reactive distillation column with different k con in the face of a ±2%step change in the production rate,respectively (Example I).(a)Positive responses and (b)negative responses.Under-dampness is presented in both the positive and negative responses with its degree inversely proportional to the controller gain of the reflux drum.Similar to Example I,there exists a high degree of asymmetry (i.e.,process nonlinearity)between the pos-itive and negative responses.In particular,a much larger variation is caused in the negative response in case k con is equal to 0.2s −1than in case k con is equal to 1.0and 2.5s −1.It is apparently related to the slow dynamics of the reflux drum.Although not shown here,the difference in steady states can finally vanish after a long time period.Non-minimum phase behavior (i.e.,initial inverse response)is observed,which is evidently attributed to the existence of a side reaction.It is noted here that the severity of process nonlinearity and non-minimum phase behavior is also inversely proportional to the controller gain of the reflux drum.Fig.11gives the open-loop transient responses of the totally refluxed ideal reactive distillation column with different k con ,when it is in the face of a ±2%step change in the feed flow rate of reactant A,respectively.Extremely similar to Example I,the impact from the variation of the controller gain of the reflux drum is hardly observed in this situation.4.3.Evaluation of closed-loop control performanceFig.12illustrates the detailed control scheme for the totally refluxed ideal reactive distillation column with a main and a side reactions.In the light of the steady-state composition profile given in Fig.9,stage 11is chosen and controlled with the feed flow rate of reactant A to regulate the stoichiometric balance between theTable 4Controller parameters for Example II.ParameterControl loopReflux drum levelBase levelStoichiometric balanceBottom Ck0.2/1.0/2.50.2 4.58 2.7T i (min)–––16.67W.Liu et al./Journal of Process Control 22 (2012) 1182–11971189Table 3Physicochemical properties and operating conditions of Example II.ParameterValueColumn pressure (bar)8.0Number of stagesRectifying section 0Reactive section 9Stripping section 5Liquid hodlup (mol)Condenser 20,000.0Column tray 1000.0Reboiler 20,000.0Main reaction activation energy (J mol −1)Forward 125,520Backward 125,520Side reaction activation energy (J mol −1)Forward 125,520Backward 125,520Specific main reaction rate at 366K (mol s −1mol −1)Forward 0.008Backward 0.0004Specific side reaction rate at 366K (mol s −1mol −1)Forward 0.005Backward 0.0002Feed flow rate (mol s −1)A 12.63B 12.82Feed locationA 10B 2Feed thermal conditionA 1.0B1.0Relative volatility (A:B:C:D)8:4:2:1Heat of reaction (J mol −1)Latent heat of vaporization (J mol −1)29,053.7Bottom product specification (C,mol%)98Vapor pressure constantsA (A vp /B vp )12.3463/3862B (A vp /B vp )11.6531/3862C (A vp /B vp )10.9600/3862D (A vp /B vp )10.2669/3862reactants,A and B.A P-only controller is again used here.The feed flow rate of reactant B is the production rate handle and flow con-trolled.The controller parameters are tabulated in Table 4.The servo responses of the totally refluxed ideal reactive distil-lation column are illustrated in Fig.13,when there is a ±0.3mol%step change in the set-point of bottom control loop,respectively.In case k con is set to be 0.2s −1,while the totally refluxedidealFig.8.Scheme of a totally refluxed ideal reactive distillation column with one main and one side reactions (Example II).reactive distillation column settles down with a large deviation in the face of the positive change in the set-point of bottom con-trol loop,a magnified oscillation occurs in the face of the negative change in the set-point of bottom control loop.In case k con is set to be 1.0and 2.5s −1,fairly smooth operation can be achieved for both the positive and negative changes in the set-point of bottom control loop.The responses with k con as 2.5s −1outperform those with k con as 1.0s −1.Fig.14presents the regulatory responses of the totally refluxed ideal reactive distillation column in the face of a ±2%step change in the feed flow rate of reactant B,respectively.When k con is set to be 0.2s −1,rather oscillating responses are obtained for both the posi-tive and negative changes in the feed flow rate of reactant B.With relatively tight inventory control of the reflux drum (i.e.,1.0and 2.5s −1),sharp improvement in control performance is achieved,giving much smaller overshoots and shorter settling times.A coun-terintuitive phenomenon is observed here,i.e.,the heat duty of reboiler changes inversely proportional to the production rate.It is considered to be caused by the existence of input multiplicities in the totally refluxed ideal reactive distillation column.The transi-tion between the inherent multiple steady states distorts actually the relationship between the production rate and the heat duty of reboiler.5.Example III:A high-purity ethylene glycol reactive distillation column5.1.Process descriptionEthylene glycol (C 2H 6O 2)is produced by hydration of ethylene oxide (C 2H 4O),i.e.,the main reaction:C 2H 4O(EO)+H 2O →C 2H 6O 2(EG), H R =–80.0×103J mol −1(10.1)r m =3.15×1015exp−9547Tx EO x W (10.2)。