Evaporator Fouling Tendencies of Thin Stillage and Concentrates From the Dry Grind Process

ABSTRACT

In the United States, more than 200 maize processing plants use multiple-effect evaporators to remove water from thin stillage and steepwater during dry grind and wet milling processes, respectively. During the dry grind process, unfermentables are centrifuged and the liquid fraction, thin stillage, is concentrated in multiple effect evaporators. Evaporator fouling occurs during thin stillage concentration and may be from deposition of proteins, fat, fiber, and/or carbohydrates on evaporator surfaces. Studies on evaporator fouling from maize processing streams are limited and fundamental causes are not well understood. Therefore, the overall objective was to investigate effects of compositional variation on evaporator fouling during thin stillage concentration. Effects of total solids during evaporator concentration, removal of post fermentation oil, corn oil and glycerol addition, and overall plant operation were studied. Thin stillage had lower fouling rates compared to evaporator concentrates. Addition of postfermentation corn oil (0.5 to 1.0% added) increased thin stillage fouling rates, but at higher oil concentration (1.5% added), rates decreased. At 10% solids content in evaporator concentrates, oil recovery had no influence on fouling rates. Glycerol addition (1%) to thin stillage increased fouling rates. Simultaneous plant shutdown and evaporator cleaning decreased subsequent fouling rates.     

The heat and mass transfer performance of facile synthesized silica gel/carbon-fiber based consolidated composite adsorbents developed by freeze-drying method

A series of experimental investigations had been performed to analyze the heat and mass transfer performance for two novel types of silica-based consolidated composite adsorbents developed by the freeze-drying method. The first type of adsorbent is silica gel consolidated with carboxymethyl cellulose (CMC) (SC), while the other is silica gel consolidated with CMC and carbon fiber powder (SCC). Results indicate that the thermal conductivity of consolidated composite adsorbents increases with the mass proportion of carbon fiber powder, while it decreases with the increasing moisture content in the preparation process of the adsorbents. When the mass ratio of silica gel, CMC, and carbon fiber powder is 4:1:4, the highest thermal conductivity of consolidated composite adsorbent obtained from experiments reaches 1.66 W m^?1 K^?1, which is 13.4 times greater than that of pure silica gel. Furthermore, the results of macroporous properties analysis of typical samples including SC20 and SCC20 (where the 20 means that the undried samples have a water content of 20% by mass during the preparation process) show that heat transfer additives effectively improve the macroporous porosity and permeability of the consolidated composite adsorbents. The study on adsorption dynamic performance indicates that the freeze-drying method helps to improve the adsorption performance including adsorption rate and equilibrium water uptake. The experimental results also show that the mass transfer coefficient K of the two typical samples are approximately stable at 5 × 10^?3 s^?1 when the adsorption temperature is ranged between 30 and 40°C, which are almost twice the corresponding values of the samples developed by heating–drying method. Therefore, the proposed approach which is the consolidation with heat transfer additives combined with freeze-drying method is effective for simultaneously enhancing the heat and mass transfer performance of the silica gel adsorbents.     

Deposit Formation in Evaporation of a Pulp Mill Effluent

A preliminary study was undertaken of the fouling of clarified wastewater from a “zero”-liquid discharge bleached chemi-thermo-mechanical pulp mill. This work concerned the fouling process that occurs in mechanical vapor recompression evaporators, which comprise the first stage of the evaporation and concentration system. The clarified wastewater contains dissolved and suspended solids, both of which increase as the liquor is concentrated. Solids contain roughly 20% mineral matter and the remainder is organic material. Thermal fouling measurements were made in a countercurrent double-pipe exchanger in which liquors of three different concentrations were heated by condensing steam. The decline in heat transfer coefficient was tracked over periods of several days at fixed steam temperature and fluid velocity. Fouling increased with both liquor concentration and steam temperature. Soft, sludge-like deposits that contained mainly organic material were found. The inorganic fraction was about 25% and consisted primarily of calcium, magnesium, and silicon. The sources of the inorganic fraction in the deposits are discussed, and deposit analyses are compared with those of the solids present in the liquor.     

Initiation of CASO4 Scale Formation on Heat Transfer Surfaces under Pool Boiling Conditions

The success of innovative fouling mitigation techniques such as ion implantation depends upon the early stage of scale formation on the heat transfer surface. This is because the first crystalline nuclei that appear on the surface during the initial period dictate how fouling would develop in latter stages. In this study, the initial period of deposition of calcium sulfate on heat transfer surfaces has been investigated under pool boiling conditions. The independent variables were heat flux and calcium sulfate concentration. The experimental results show that the time until the heat transfer coefficient reaches its intermediate maximum decreases with an increasing concentration and heat flux, and is also significantly affected by the surface finish. Neural network architectures were utilized to correlate the experimental results during the initial deposition period. A satisfactory agreement between predicted and measured heat transfer coefficients has been achieved with an average error of 8.7%.     

Heat Exchanger Fouling in Phosphoric Acid Evaporators

Multistage shell and tube evaporators are frequently used in phosphoric acid plants to increase the concentration of dilute phosphoric acid to 52–55 wt% P₂O_5. The concentrated phosphoric acid solution is supersaturated with respect to calcium sulfate. As a result, part of the calcium sulfate in the liquor deposits on the heat exchanger tube walls. Because the thermal conductivity of these scales is very low, thin deposits can create a significant resistance to heat transfer. Therefore, regular cleaning of heat exchangers is required, frequently at shorter than biweekly intervals. As the major costs in modern phosphoric acid plants are the cost of energy, a thorough understanding of the fouling kinetics and of the effects of various operational parameters on the behavior of calcium sulfate is required to improve operation and design of the shell and tube heat exchangers, which are extensively used. In this investigation, a large set of heat exchanger data was collected from shell and tube heat exchangers of the phosphoric acid plant of the Razi Petrochemical Complex in Iran, and the fouling deposits were analyzed with respect to appearance and composition. The overall heat transfer coefficients and fouling resistances were evaluated at different times, and a kinetic model for the crystallization fouling was developed. It is shown that the crystallization rate constant obeys an Arrhenius relationship with an activation energy of 57 kJ/mol. The average absolute error of 12.4% shows that the predictions of the suggested model are in good agreement with the original plant data.     

Crosslinked sulfonated poly(arylene ether sulfone)/silica hybrid membranes for high temperature proton exchange membrane fuel cells

Sulfonated poly(arylene ether sulfone) copolymer is synthesized via nucleophilic step polymerization of sulfonated 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl sulfone and phenolphthalin monomers in the presence of potassium carbonate. The copolymer is blended with various amounts of silica particles to form organic–inorganic composite membranes. Esterification reaction is carried out between silica particles and the sulfonated polymer chains by thermal treatment in the presence of sodium hypophosphite, which catalyzed the esterification reaction. The composition and incorporation of the sulfonated repeat unit are confirmed by ¹H NMR. The water uptake, proton conductivity, and thermal decomposition temperature of the membranes are measured. The silica content in the polymer matrix and the effect of esterification are evaluated. All composite membranes show better water uptake and proton conductivity than the unmodified membrane. Moreover, the membranes are tested in a commercial single cell at 80 °C and 120 °C in humidified H₂/air under different relative humidity conditions. The composite membrane containing 10% (w/w) silica shows the best performance among the prepared membranes especially under high temperature and low humidity conditions.     

基于格子Boltzmann方法的微通道受热表面析晶污垢模拟

针对现有的污垢析晶沉积模型不能有效模拟真实污垢生长的问题,建立了一种引入析晶沉积动力学模型的多物理场耦合数值模型。模型基于格子Boltzmann方法和有限差分方法,模拟了微通道非等温热表面上近壁面处的沉积物溶质质量浓度分布和污垢生长过程,研究了流速、壁温和沉积物溶质质量浓度对微通道热表面污垢析晶沉积的影响。结果表明：沉积初始时刻流速和壁温对近壁面沉积物溶质质量浓度分布具有不同程度的影响,随着污垢不断生长,污垢-流体界面处的析晶沉积速率减小;相比于流速,沉积物溶质质量浓度对污垢热阻的影响更为显著。     

Crude Oil Fouling Deposition,Suppression, Removal,and Consolidation—and How to Tell the Difference

ABSTRACT

Crude oil fouling on heat transfer surfaces is often described as the result of two competing mechanisms: a deposition and a deposition-offsetting mechanism. There is uncertainty about whether the offsetting mechanism is suppression (due inhibition of attachment or back-diffusion of foulant from near the wall into the bulk) or removal of foulant already deposited, due to (i) difficulties in experimentally identifying and isolating the key phenomena and (ii) the cumulative measurement of deposition rates by monitoring thermal exchange rates (or resistance) alone. Here, the question is addressed of whether it is conceptually possible to distinguish such phenomena, and if so, in which conditions. A recently developed two-dimensional (2D) deposit model and a thermohydraulic model of a heat exchanger tube are used to assess the system response to removal, suppression, aging, and consolidation (for which a new model is proposed). It is shown that while suppression or removal lead to undistinguishable behavior during overall deposit growth, thermal and hydraulic responses will differ in certain conditions, for which an experimental procedure is suggested. Simultaneous consideration of thermal and hydraulic effects and accurate characterization of the deposit aging and consolidation processes are suggested as a way to allow the unambiguous identification of the dominant deposition-offsetting mechanism.     

油田污水水垢控制器除防垢机理研究及其应用效果分析

近年来,由于油田采出液含水率上升,含油污水深度处理越来越困难,采用常规含油污水处理系统处理污水通常会造成过滤罐阻塞和溢流,从而导致其处理能力下降。高频电磁水垢控制器是一种主要用于除垢及防垢的装置,在油田污水处理系统中得到广泛应用。其机理是向污水加一足够强度电压后,感应偶极矩的出现使污水介质的硬度下降,流动性变好;在交替变化的电磁场中,带有正负电荷的水分子团被反复极化以至于和外加电磁场发生共振,最终成为稳定的双水分子,其使过去形成的片状方解石晶体形成细小、松软的针状的文石晶体,并随水流冲走;双水分子渗透到污垢与容器壁之间,在动态溶解平衡过程中利用其与金属材料膨胀率的不同,使原有的污垢逐渐松软、龟裂、脱落、排除。在过滤罐入口端安装高频电磁水垢控制器后,结垢沉积量和结垢沉积速率略有降低,说明水垢控制器在抑制垢沉积上有一定效果;水垢控制器前端沉积物主要为钙垢,后端沉积物主要为铁垢。     

Thermal conductivities study on silica aerogel and its composite insulation materials

This paper presents a theoretical and experimental study on thermal conductivities of silica aerogel, xonotlite-type calcium silicate and xonotlite–aerogel composite insulation material. The transmittance spectra of silica aerogel and xonotlite-type calcium silicate samples are obtained through FTIR measurements. The corresponding extinction coefficient spectra of the three materials are then obtained by applying Beer’s law. The thermal conductivities of aerogel, xonotlite-type calcium silicate, and xonotlite–aerogel composite insulation material are measured from 300 to 970 K and from 0.045 Pa to atmospheric pressure with the transient hot-strip (THS) method. The thermal conductivity models developed for coupled heat transfer of gas and solid based on the unit cell method are compared with the experimental measurement results. It is shown that the effective thermal conductivity models matches well with the experimental data. The specific spectral extinction coefficients of xonotlite-type calcium are larger than 10 m² kg^?1, and the specific spectral extinction coefficients of aerogel are larger than 7 m² kg^?1 over the whole measured spectra. The density of xonotlite-type calcium silicate is the key factor affecting the effective thermal conductivity of xonotlite–aerogel composite insulation material, and the density of aerogel has little influence. The effective thermal conductivity can be lowered greatly by composite of the two materials at an elevated temperature.     

Investigation of adhesion of CaCO3 crystalline fouling on stainless steel surfaces with different roughness

Fouling adhering experiments on AISI 304 stainless steel surfaces with different roughness had been performed in boiling supersaturated calcium bicarbonate solution. The effect of surface roughness on adhesion of fouling is limited, and the adhesion of fouling does not have a simple linear relationship with the surface roughness of samples. The surface with roughness in middle is more easily induced to form “transitional interface” which connects the fouling and matrix surface. It is also found that the crystalline types of fouling are changed in the fouling process due to the variation of metallic ions in reaction solution.     

Calcium Phosphate Scale Formation in Power Station Condensers Fed by Cooling Towers: A Case of When Not to Use Scaling Indices

Abstract

Unexpected fouling in condensers on Central Electricity Generating Board power stations operating on the river Trent in the UK in the 1970s prompted an extensive investigation of the phenomenon. Fouling was caused by deposition of calcium phosphate rich scale on the cooling water side. A fouling test rig was specially constructed to study the performance of different chemical treatments. The rig ran two tubes in parallel, one with undosed water, and the latter’s data sets from over 100 “control” tests were analyzed to determine the mechanism and rate of fouling. The trends could not be explained in terms of conventional scaling indices. Insight into the mechanism was provided by separating precipitation (loss from solution) and deposition (adhesion of some of the precipitated mass to the heated surface): scaling was found to be caused by the deposition of particulates in the recirculating cooling water, driven by the change in pH as the water went through the evaporative cooling stage. Quantitative expressions for fouling were generated from tests on 1.83?m long tubes and were found to give a reasonable prediction of the fouling behavior observed on a full sized (18.3?m long) single condenser tube on an operating condenser. The results indicated that recirculating water systems need to be approached very differently to once-through systems, and the use of scaling indices for such systems is not recommended.     

CaCO3垢的形成对池核沸腾传热的影响

在一水平圆形加热表面上通过实验考察了饱和池核沸腾和过冷池核沸腾时CaCO3垢的生成对传热的影响。结果表明，在饱和池核沸腾和过冷池核沸腾的初始阶段沸腾传热系数均呈先降低后升高、达到一个最大值后稳定降低的趋势，而且在初始阶段出现了负污垢热阻现象。在相同操作条件下，过冷池核沸腾传热系数明显低于饱和池核沸腾传热系数。在分析污垢的生成和生长影响表面活化中心的基础上，对污垢的形成对沸腾传热的影响进行了机理分析。     

Mineral scale formation and mitigation on metals and a polymeric heat exchanger surface

An experimental set-up was built to study heat transfer fouling of different pipe materials used in heat exchangers. Fouling mitigation investigations using wood pulp fibres in suspension in the fouling liquid were also performed. The new set-up allows progressive visual observation of fouling with time together with a recorded history under the same solution conditions. On completion, the tube under investigation could be removed to obtain quantitative data on the progressive build up of the deposit as well as the composition of the deposit.The experimental technique involved a pipe test specimen being centrally located in a cylindrical tank concentric with a vertical agitator to give constant and uniform flow conditions near the tube surface. The investigation of calcium sulphate deposition on four different metal surfaces (copper, aluminium, brass and stainless steel SS 316 respectively) and a polycarbonate surface reveals that the fouling increases with time but at a decreasing rate. The deposition on a metal surface can be seen to increase with increasing thermal conductivity and decreasing total surface energy over the range of experiments. Low surface energy material such as polycarbonate causes less attraction to the floating crystals and receives less deposition in comparison to the SS surface.Bleached Kraft softwood fibres at various concentrations were added to the solution to examine their effects on fouling. The results indicate that fouling is reduced as fibre concentration increases. It was also found that the fouling on stainless steel, brass and copper surfaces were all retarded in presence of fibre in the solution.     

Impact of Tube Surface Properties on Crystallization Fouling in Falling Film Evaporators for Seawater Desalination

ABSTRACT

Crystallization fouling on heat transfer surfaces is a severe problem and a complex phenomenon in multiple-effect distillation plants with horizontal tube falling film evaporators for seawater desalination. The choice of tube material affects the wettability, the adhesion forces between surface and deposit, and the induction time of crystallization fouling. The effects of surface properties on crystallization fouling from seawater have been investigated in a horizontal tube falling film evaporator in pilot plant scale. Experiments were performed with artificial seawater and various tube materials. The tube surfaces were characterized by measuring surface roughness and contact angles and by determining surface free energies. The tube materials show qualitative and quantitative differences with respect to scale formation. The interfacial defect model was applied to the system. Spreading coefficients of CaCO₃ scale on the aluminum alloys 5052 and 6060 and stainless steel grade 1.4565 were calculated to be higher than those on copper–nickel 90/10 and aluminum brass, but the quantities of CaCO₃ scale measured on the tube surfaces were much lower compared to CuNi 90/10 and aluminum brass. The application of advanced approaches such as the interfacial defect model depends on the precise knowledge of interfacial free energies, which are very difficult to find. However, results suggest that more similar values of the interfacial free energies of heat transfer surface and deposit lead to increased scale formation.     

A study of capillary-assisted evaporators

The paper presents a comparative study of the effect of porous layer parameters on the thermal performance of capillary-assisted evaporators. The results show that there are optimum particle sizes that are associated with maximum boiling heat rates and heat transfer coefficients. The results also show that the layer thickness has monotonic effect on the evaporators’ performance but its impact is less pronounced compared to that of the particle size. The trends are explained in terms of the contradicting effects that exist within the layer. Agreement in trend, and to a lesser degree in value, is obtained between the analytical and experimental results with the discrepancy explained in terms of the inaccuracies of the empirical formulae used and the effect of condensation on the tube wall thermal resistance. Boiling heat transfer coefficients of up to 5 kW/m² °C were achieved.     

Simulation of the effect of scale deposition on a geothermal turbine

Dissolved chemicals contained in geothermal steam can lead to corrosion, erosion and deposition of scale on turbine blades, reducing their useful life. In addition, deposits on the blading system reduce the flow area of the turbine. The first-stage nozzle group is typically most affected by deposition of scale although scale may be present in other parts of the system. The most common deposits are of silica and calcium carbonate. This decreases the output capacity and efficiency of the turbine. This paper presents the results of simulations on the effect of scale deposition in the first-stage nozzle group on the steam pressure before and after the first stage, output capacity and efficiency of the turbine. By measuring the steam pressure before and after the first stage the change in the flow area can be estimated. A method of monitoring the percentage of nozzle plugging in real time is proposed. The method can be applied to any turbine that is susceptible to scale deposition.     

Study of the Effect of Fin-and-Tube Heat Exchanger Fouling on its Structural Performance

This paper presents the thermal and structural analysis of high temperature fin-and-tube heat exchanger. Water flowing in tubular space and flue-gas flowing in the intertubular space, were considered as working fluids. The effect of limescale fouling on thermal and structural performance of heat exchanger was studied. The analysis considered an industrial heat exchanger, which failure occur from time to time. The expert inspection, after the failure indicated the existence of fouling layer within the heat exchanger tubes. In order to understand the reasons of heat exchanger failure, a detailed fluid flow analysis (both in the tubular and intertubular spaces) was performed. The analysis indicated that the silicate limescale fouling layer with thermal conductivity of 0.35 W/(mK) and thickness up to 1.5 mm existing in the tube, may increase the tube wall temperature even more than 150°C. The study also includes the impact of outer tube wall surface fouling with thickness of 0.2 mm and heat transfer coefficient of 2 W/(mK). As a result, the compressible stresses may increase over three times compared to the situation where the tube wall fouling does not exist.     

Modeling and Prediction of Shell-Side Fouling in Shell-and-Tube Heat Exchangers

Fouling is a challenging, longstanding, and costly problem affecting a variety of heat transfer applications in industry. Mathematical models that aim at capturing and predicting fouling trends in shell-and-tube heat exchangers typically focus on fouling inside the tubes, while fouling on the shell side has generally been neglected. However, fouling deposition on the shell side may be significant in practice, impairing heat transfer, increasing pressure drops, and modifying flow paths. In this paper, a new model formulation is presented that enables capturing fouling on the shell side of shell-and-tube heat exchangers including the effect of occlusion of the shell-side clearances. It is demonstrated by means of an industrial case study in a crude oil refinery application. The model, implemented in an advanced simulation environment, is fitted to plant data. It is shown to capture the complex thermal and hydraulic interactions between fouling growth inside and outside of the tubes, the effect of fouling on the occlusion of the shell-side construction clearances, and to unveil the impact on shell-side flow patterns, heat transfer coefficient, pressure drops, and overall exchanger performance. The model is shown to predict the fouling behavior in a seamless dynamic simulation of both deposition and cleaning operations, with excellent results.     

Preparation of functional copolymer based composite membranes containing graphene oxide showing improved electrochemical properties and fuel cell performance

The objective of this work is to prepare a functional copolymer of poly(acrylonitrile)-co-poly(2-Acrylamido-2-methyl-1-propanesulfonic acid) (PAN-co-PAMPS) and impregnation of graphene oxide (GO) into the copolymer followed by crosslinking to prepare conetwork composite membranes by simple and cost effective solution casting method and evaluating their structural, morphological, thermal, and mechanical properties. The successful incorporation of different amounts of GO content (0.1–1 wt%) within the polymer matrix was confirmed by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The mechanical properties of the prepared crosslinked composite membranes are found to be greatly enhanced by the addition of GO in the copolymer matrix. The thermogravimetric analysis (TGA) demonstrated considerable improvements in thermal stability for the composite membrane with low GO content. The effect of loading of GO in the copolymer matrix on proton conductivity and fuel cell performance has been studied systematically. The membranes prepared by mixing with 0.5 wt% GO in the copolymer followed by crosslinking exhibited maximum ionic conductivity (K^m), lower methanol permeability (P_M), and higher relative selectivity. This observed P_M value is much lower range from 3.02 × 10^?7 to 11.9 × 10^?7 cm²/s compared to the Nafion® 117 membrane (22 × 10^?7 cm²/s). The fuel cell performance in terms of maximum power density and current density and the durability of the crosslinked composite membranes have also been evaluated here. Low P_M, high K^m, and high selectivity values show that functional co-polymer/GO crosslinked co-network composite membrane is a promising alternative membrane separator to replace the expensive Nafion® 117 for proton exchange membrane fuel cells (PEMFCs) application.