Final Report: Freeze Concentration for Zero-Effluent Processes

EPA Grant Number: R825511C070
Subproject: this is subproject number 070 , established and managed by the Center Director under grant R825511
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: HSRC (1989) - Northeast HSRC
Center Director: Sidhu, Sukh S.
Title: Freeze Concentration for Zero-Effluent Processes
Investigators: Botsaris, Gregory D. , Quain, Ru-Ying
Institution: Tufts University
EPA Project Officer: Hahn, Intaek
Project Period: January 15, 1995 through January 14, 1997
RFA: Hazardous Substance Research Centers - HSRC (1989) RFA Text |  Recipients Lists
Research Category: Hazardous Substance Research Centers , Land and Waste Management

Objective:

Freeze concentration involves the volume reduction of an aqueous solution by partial freezing of the water and subsequent separation of the resulting ice crystals. The goal of this project is to demonstrate the feasibility of the Tufts Freeze Concentration process in the treatment of wastewater containing contaminants in general and in particular of effluents from the bleaching plant of a paper pulp mill. More specifically to demonstrate that the Tufts process, involving the use of ultrasounds for the nucleation stage of the ice crystals, provides ice of high purity in terms of adsorbable organic halides (AOX) and non - process elements(NPE). In addition to collect data in the laboratory needed for the subsequent scaling up of the process to the pilot plant stage and eventually to industrial units capable of handling the high effluent volumes encountered in pulp mills.

Summary/Accomplishments (Outputs/Outcomes):

Rationale: The effluents from pulp and paper mills are one of the main sources of pollution. The concern about AOX, dioxins, and other toxic compounds in these effluents is driving the use of Total Chlorine Free (TCF) bleaching in European pulp mills. In the United States, however, the paper market and cost analysis orients the industry towards Elemental Chlorine Free (ETC) process. In this era of tightening emission rules and movement toward zero or minimum effluent process, traditional volume reduction process, like evaporation and distillation, were proven inadequate for the concentration of effluents containing AOX, that is hundreds of volatile organic compounds (VOC) with a wide spectrum of volatilities. The freeze concentration, however, is based on the crystallization of ice which is nondiscriminating toward all solutes. The high purity of the ice provides also pure water for recycling (particularly where the recycled water will substitute fresh water usage) and in the process allows for bleach plant closure without the adverse effects of NPE and organic compounds build-up in the recycled stream.

Approach: The experiments were conducted with a bench scale batch apparatus. The following characteristics were incorporated in it, based on the experience from the previous freeze concentration technology. 1.Indirect cooling-- Previous works on desalination by direct-cooling freeze concentration achieved inadequate purification factors of only 70 and 80 much lower than 1000 by indirect cooling. 2. Decoupling nucleation and crystal growth-- In previous attempts to use freeze concentration in pulp mills, including the HDP process, the nucleation and the growth of ice crystals took place in the same crystallizer. This resulted in serious ice -scaling and - crystal washing problems. 3. Ultrasonic nucleation-- The current industrial process for the freeze concentration of fruit juices (NIRO process) employs a scraped-cooling-syrface nucleator. Its weaknesses for use in the effluents include low productivity, high cost and inability to scale-up.

Status: (For the period Oct, 1 1995 to Sept. 30,1996). Experiments were conducted in the batch apparatus with both a model system in which the contaminant was simulated by a specific stable compound (glucose) and with an actual bleach effluent. In both cases large ice crystals of high purity were obtained. In the case of the effluent from bleaching unit of a pulp mill, the concentrations of the chlorides in the ice were 1.6-3.9 ppm and of AOX 0.043-0.14 ppm. Experiments to determine the maximum allowable temperature difference between coolant and solution in an indirect cooler were also conducted.

Client/Users: Kraft pulp mills in the United States with chlorine or ECF bleaching units will be able with the freeze concentration process, to achieve a low AOX concentration in the effluents which is comparable to that from a TCF bleaching process. Our process could be applied also to the effluents from other industries, most notably to the volume reduction of radioactive wastes.

Journal Articles:

No journal articles submitted with this report: View all 1 publications for this subproject

Supplemental Keywords:

Freeze Concentration Technology, dioxins., Scientific Discipline, Water, TREATMENT/CONTROL, Sustainable Industry/Business, Chemical Engineering, Wastewater, Environmental Chemistry, Technology, Economics and Business, New/Innovative technologies, Environmental Engineering, hazardous liquid waste, freeze concentration, industrial wastewater, clean technologies, zero discharge cycles, chlorine alternative, emissions control technology, pulp and paper industry, adsorbable organic halides, effluents, innovative technologies, zero effluent processes, aqueous waste stream

Progress and Final Reports:

Original Abstract
  • 1995

  • Main Center Abstract and Reports:

    R825511    HSRC (1989) - Northeast HSRC

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R825511C001 Development of Mechanisms and Kinetic Models on Formation of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Aromatic Precursors
    R825511C002 Real-Time Monitoring and Control of Emissions from Stationary Combustors and Incinerators
    R825511C003 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
    R825511C004 Investigation into the Effectiveness of DNAPL Remediation Strategies in Fractured Media
    R825511C005 Advanced Leak Detection and Location Research: Extending the SERDP-funded Technical Base
    R825511C006 Three-Dimensional Geostatistical Site Characterization with Updating
    R825511C007 Anaerobic Biodegradation of PAHs in Soils and Dredged Sediments: Characterizing, Monitoring and Promoting Remediation
    R825511C008 Substrate Accelerated Death and Extended Lag Phases as Causes of the Recalcitrance of Halogenated Compounds in Anoxic Environments
    R825511C009 Fate and Transport of Nonionic Surfactants
    R825511C010 In Situ Degradation of Petroleum Hydrocarbons and PAHs in Contaminated Salt Marsh Sediments
    R825511C011 Design and Operation of Surfactant-Enhanced Bioslurry Reactors
    R825511C012 Experimental Study of Overland Transport of Cryptosporidium parvum Oocysts
    R825511C013 Development of a Framework for Evaluation of Leaching from Solid Waste
    R825511C014 Use of a New Leaching Test Framework for Evaluating Alternative Treatment Processes for Mercury Contaminated Mixed Waste (Hazardous and Radioactive)
    R825511C015 Field Pilot Test of In Situ Ultrasonic Enhancement Coupled With Soil Fracturing to Detoxify Contaminated Soil
    R825511C016 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
    R825511C017 Field Demonstration of the Use of Reactive Zero-Valence Iron Powder to Treat Source Zone Sites Impacted by Halogenated Volatile Organic Chemicals
    R825511C018 Technology Transfer of Continuous Non-Methane Organic Carbon (C-NMOC) Analyzer
    R825511C019 Field Sampling and Treatability Study for In-Situ Remediation of PCB's and Leachable Lead with Iron Powder
    R825511C020 Experimental and Modeling Studies of Chlorocarbon Incineration, PIC Formation, and Emissions Control
    R825511C021 Experimental Studies and Numerical Modeling of Turbulent Combustion During Thermal Treatment of Hazardous Wastes: Applied Research for the Generation of Design and Diagnostic Tools
    R825511C022 Electrochemical Sensor for Heavy Metals in Groundwater - Phase IV
    R825511C023 Novel Molecular Tools for Monitoring In-Situ Bioremediation
    R825511C024 Surfactant-Enhanced Bioremediation of Soils in the Presence of an Organic Phase
    R825511C025 Enhanced Microbial Dechlorination of PCBs and Dioxins in Contaminated Dredge Spoils
    R825511C026 Toward A Risk-Based Model for Bioremediation of Multicomponent NAPL Contaminants
    R825511C027 Removal and Recovery of VOCs and Oils from Surfactant-Flushed Recovered Water by Membrane Permeation
    R825511C029 Field Pilot Test of In-Situ Ultrasonic Enhancement Coupled With Soil Fracturing to Detoxify Contaminated Soil in Cooperation with McLaren/Hart Environmental Engineers at the Hillsborough, NJ Site
    R825511C030 In-Situ Field Test of Electroremediation of a Chromate-Contaminated Site in Hudson County, New Jersey
    R825511C031 Electrokinetic Removal of Heavy Metals and Mixed Hazardous Wastes from Partially and Fully Saturated Soils
    R825511C032 Effects of Clay Charge and Confining Stresses on Soil Remediation by Electroosmosis
    R825511C033 Assessment of Surfactant Enhanced Bioremediation for Soils/Aquifers Containing Polycyclic Aromatic Hydrocarbons (PAHs)
    R825511C034 In-Situ Bioremediation of Organic Compounds: Coupling of Mass Transfer and Biodegradation
    R825511C035 Investigation into the Effectiveness of DNAPL Remediation Strategies in Fractured Media
    R825511C036 Field Pilot Scale Demonstration of Trench Bio-Sparge: An In-Situ Groundwater Treatment Technology
    R825511C037 In-Situ Reductive Dehalogenation of Aliphatic Compounds by Fermentative Heterotrophic Bacteria
    R825511C038 The Effect of Carbon-Nitrogen Ratios on Bacterial Transport and Biodegradation Rates In Soils
    R825511C039 Ultrasonic Enhancement of Soil Fracturing Technologies for In-Situ Detoxification of Contaminated Soil
    R825511C040 Full Field Demonstration of Integrated Pneumatic Fracturing and In-Situ Bioremediation
    R825511C041 Determination of Adsorption and Desorption Behavior of Petroleum Products on Soils
    R825511C042 Evaluation of the Potential for Complete Bioremediation of NAPL-Contaminated Soils Containing Polycyclic Aromatic Hydrocarbons (PAHs)
    R825511C043 Characterization of Subsurface NAPL Distributions at Heterogeneous Field Sites
    R825511C044 Development of a Thermal Desorption Gas Chromatograph/Microwave Induced Plasma/Mass Spectrometer (TDGC/MIP/MS) for On-site Analysis of Organic and Metal Contaminants
    R825511C045 Using Trainable Networks for a Three-dimensional Characterization of Subsurface Contamination
    R825511C046 Application of Advanced Waste Characterization to Soil Washing and Treatment
    R825511C047 Electrochemical Sensor for Heavy Metals in Groundwater Phase III
    R825511C048 Improved Luminescence Sensors for Oxygen Measurement
    R825511C049 Preconcentration, Speciation and Determination of Dissolved Heavy Metals in Natural Waters, using Ion Exchange and Graphite Furnace Atomic Absorption Spectrometry
    R825511C050 Experimental and Modeling Studies of Chlorocarbon Incineration and PIC Formation
    R825511C051 PIC Emission Minimization: Fundamentals and Applications
    R825511C052 Project Title: Development of a Two Stage, Pulse Combustion, VOC Destruction Technology
    R825511C053 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
    R825511C054 FTIR Analysis of Gaseous Products from Hazardous Waste Combustion
    R825511C055 Toxic Metals Volatilization for Waste Separation and Real-time Metals Analyses
    R825511C056 Mixed Metal Removal and Recovery by Hollow Fiber Membrane-Based Extractive Adsorber
    R825511C057 Removal of Volatile Organic Compounds (VOCs) from Contaminated Groundwater and Soils by Pervaporation
    R825511C058 Simultaneous SO2/NO Removal/Recovery by Hollow Fiber Membrane
    R825511C059 Superfund Sites and Mineral Industries Method
    R825511C060 Soil Washing of Mixed Organics/Metal Contamination
    R825511C061 Removal of Cesium, Strontium, Americium, Technetium and Plutonium from Radioactive Wastewater
    R825511C062 Development of a Method for Removal of Nonvolatile Organic Materials from Soil using Flotation
    R825511C063 Recovery of Evaporative Fuel Losses by Vapor Permeation Membranes
    R825511C064 Surfactant Selection Protocol for Ex Situ Soil Washing
    R825511C065 Biofiltration for the Control of Toxic Industrial VOCs Emissions
    R825511C066 Catalytic Oxidation of Volatile Organic Compounds in Water
    R825511C067 Soil Washing for Remediating Metal Contaminated Soils
    R825511C068 Aqueous Absorption and Kinetics of NO by Strong Oxidizing Agents
    R825511C069 Remediation of Dredging Spoils
    R825511C070 Freeze Concentration for Zero-Effluent Processes
    R825511C071 Life Cycle/Pollution Prevention Response to Executive Order 12856
    R825511C072 Faster Better, Cheaper Hazardous Waste Site Characterization and Cleanup: an Adaptive Sampling and Analysis Strategy Employing Dynamic Workplans
    R825511C073 Development of a Comprehensive Computer Model for the Pneumatic Fracturing Process
    R825511C074 Technology Demonstration and Validation of CFAST Field Analytical Instrumentation for Use in Hazardous Waste Site Characterization, Clean-up and Monitoring
    R825511C075 XFLOW: Training Software Simulating Contaminant Site Characterization and Remediation