危险废物回转式流化冷渣多段焚烧系统焚烧特性研究

危险废物的处理和处置是摆在我国各级市政府面前的紧迫任务。然而我国已经运行的危险废物焚烧装置普遍存在回转窑挂壁结渣、热灼减率偏高和污染排放超标等问题,作者通过将回转窑和流化床特点相结合的方法提出了一种新型危险废物回转式流化冷渣多段焚烧处置装置。该装置采用回转窑(一燃室)、二燃室和流化床结合的热解-流化焚烧工艺,特别是采用控制窑头温度避免了回转窑挂壁结渣;采用流化冷渣装置延长未燃烬渣的焚烧时间,解决了热灼减率偏高问题;水冷式烟气急冷装置可以将烟气温度从1 100℃降到200℃,防止了二恶英的尾部低温再生成。该系统运行稳定可靠,可以处理医疗垃圾和大多数的固态和液态危险废物,实现了烟气污染物尤其是二恶英排放达到国家标准的目标。同时对该系统运行时窑头温度分布、二燃室炉膛出口氧量变化、回转窑和炉膛升温特性、燃烧室外壁温度分布等几方面运行数据都进行了详细的介绍,为危险废物焚烧炉的运行提供了宝贵的经验数据。     

Transient puffs of trace organic emissions from a batch-fed waste propellant incinerator

Emissions data have been obtained from a waste propellant incinerator. The incinerator is a dual fixed hearth, controlled air incinerator equipped with acid gas and particulate scrubbing. "Puffing" has been evident in this waste propellant incinerator by spikes in the CO concentration. Transient puffs of organics may travel down the combustion chambers and lead to stack emissions. The major conclusions from this study are that (1) transient puffs are formed due to the semi-batch feed nature of the combustion process (causing a local oxygen deficiency) and high water content of the desensitized propellant; (2) in batch-fed combustors, puffs can contribute to most of the organic emissions (which are relatively low) measured with US EPA sampling and analytical methods; (3) it is estimated that batch-fed combustion contributes up to 7-18 times more emissions than steady-state combustion will generate; (4) by applying dispersion analyses to determine the amount of oxygen deficiency in the flame zone, the combustion zone concentration of CO during batch-fed operation could be as high as 160,000 ppm, compared to a measured peak stack concentration of 1200 ppm CO; and (5) an organic sample is collected and averaged over at least a 2-h period that smooths out the transient peaks of organics emissions during batch-fed operation. For emissions that are associated with long-term potential health impacts, this is an appropriate sampling method. However, if a compound has a short-term potential health impact, it may be important to measure the time-resolved emissions of the compound.     

Emissions of Trace Products of Incomplete Combustion from a Pilot-Scale Incinerator Secondary Combustion Chamber

Abstract

Experiments were performed on a 73 kW rotary kiln incinerator simulator equipped with a 73 kW secondary combustion chamber (SCC) to examine emissions of products of incomplete combustion (PICs) resulting from incineration of carbon tetrachloride (CC14) and dichloromethane (CH2C12). Species were measured using an on-line gas chromatograph (GC) system capable of measuring concentrations of eight species of volatile organic compounds (VOCs) in a near-realtime fashion. Samples were taken at several points within the SCC, to generate species profiles with respect to system residence time. For the experiments, the afterburner on the SCC was operated at conditions ranging from fuel-rich to fuellean, while the kiln was operated at a constant set of conditions. Results indicate that combustion of CH2C12 produces higher levels of measured PICs than combustion of CC14, particularly 1, 2 dichlorobenzene, and to a lesser extent, monochlorobenzene. Benzene emissions were predominantly affected by the afterburner air/fuel ratio regardless of whether or not a surrogate waste was being fed.     

Burning Chemical Wastes as Fuels in Cement Kilns

Hazardous wastes in the environment represent one of our most serious problems. Ever increasing quantities of toxic wastes have contaminated our land, air, and water. Lack of adequate hazardous waste disposal facilities is a critical problem. Landfilling toxic wastes is no longer considered safe. The tragedy of the Love Canal has demonstrated the need for proper hazardous waste disposal facilities. The best organic chemical waste disposal method is process incineration. Cement kilns have been used for burning toxic chemical industrial wastes in Canada, Michigan, New York, Sweden, etc. Existing cement kilns, when properly operated, can destroy most organic chemical wastes. Even the most complex chlorinated hydrocarbons, including PCB can be completely destroyed during normal cement kiln operations, with minimal emissions to the environment. Burning toxic chemical wastes in cement kilns, and other mineral industries, is mutually beneficial to both industry, who generates such wastes, and to society and government, who want to dispose properly of such wastes in a safe, environmentally acceptable manner. The added benefit of energy conservation is important, since large quantities of valuable fuel can be saved in the manufacture of cement when such techniques are employed.     

Field Testing and Computer Modeling of an Oxygen Combustion System at the EPA Mobile Incinerator

The LINDE® Oxygen Combustion System has been demonstrated successfully at the EPA Denney Farm site as part of the modified EPA mobile incinerator. This paper describes the field testing results and computer modeling of the LINDE system. The oxygen system enables the EPA unit to incinerate dioxin and PCB contaminated soil at a consistent rate of 4000 lb/h—200 percent of the original maximum capacity. The pure oxygen combustion system improved the thermal efficiency of the incinerator by over 60 percent and reduced the flue gas volume dramatically. Therefore, the dust carryover problem was mitigated. The destruction and removal efficiencies of hazardous wastes exceeded EPA requirements.

The design of the proprietary burner allows the use of up to 100 percent oxygen in place of air for incineration with improvements over conventional oxy-fuel burners. As a result, the temperature distributions in the rotary kiln are uniform and NO_x emissions are low.

The oxygen combustion system, controlled by a programmable controller, provided much better response and flexibility than conventional air based systems. The system generated a stable flame and responsed well to the transient conditions of the rotary kiln. Kiln puff occurrence was virtually eliminated in the operation of the mobile incinerator.

A computer model of the incinerator was developed and used for the process design of the LINDE system. The model predicted the test results reasonably well. This model can be a useful tool in the design and operation of rotary kiln incineration systems.     

Rotary Kiln Incineration of Dichloromethane and Xylene: A Comparison of Incinerability Characteristics Under Various Operating Conditions

Comparisons are made, for the first time, between the combustion characteristics of dichloromethane and xylene in an industrial rotary kiln incinerator. The comparisons are made under different operating conditions, including variable kiln rotation rate and operation both with and without turbulence air. Continuous gas composition and temperature measurements and batch gas composition measurements were obtained from two vertical locations hear the exit region of the rotary kiln. The measurements show that there is significant vertical stratification at the exit of the kiln. Addition of turbulence air enhanced combustion conditions throughout the kiln during xylene processing. During dichloromethane processing, however, the addition of turbulence air had minimal effect and only promoted greater bulk mixing; chlorinated compounds transported from the lower kiln during operation with turbulence air were not efficiently processed in the upper kiln. Evolution of test liquids from the bed was not constant but rather was characterized by intermittent peaks. The field-scale data of this work suggest that the evolution rate of the test liquid was increased as kiln rotation rate increased. Many of the differences between xylene and dichloromethane processing during these experiments are explained by a simple stoichiometric analysis.     

Public Policy impacts on the Generation and Disposal of Hazardous Waste in New York State

A number of policies adopted by the federal government and the states have been designed to promote waste reduction or influence the choice of waste disposal technologies employed by generators of hazardous waste. Graphic analysis of smoothed time series data for hazardous wastes manifested in New York State for the period between June 1982 and February 1987 suggests that some of these policies have had the intended effects.

Significant shifts in manifested waste volumes are evident that coincide with the following policy interventions: (1) increased state waste-end tax rates; (2) state and federal landfill bans; (3) federal restrictions on burning hazardous wastes and waste oils for energy recovery; and (4) changes in the federal regulatory definition of hazardous waste. Other changes in waste generation and management appear to be attributable to such factors as state and regional economic conditions and changes in instate treatment and disposal facility capacity. Analysis of the management of specific waste types supports evidence from the graphic analysis that waste generators changed from land disposal to “higher” waste handling technologies in response to several policy interventions.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

Chemical Manufacturers Association 1984 Hazardous Waste Survey

This paper discusses the Chemical Manufacturers Association's 1984 survey of the chemical industry's hazardous waste management practices. The survey data include a breakdown of how the industry's hazardous wastes are managed, detailing generation, treatment and disposal, and cover 725 plants in 81 companies. The 1984 survey is the third CM A hazardous waste survey, and the paper discusses resultant waste treatment trends from 1981- 1984, the period covered by previous surveys. A total of 278.5 million tons of hazardous waste was treated and disposed by survey respondents. Of this, 276.8 million tons was hazardous wastewater and 1.7 million tons was solid hazardous waste. The survey solid hazardous waste total was projected to the entire industry (Standard Industrial Code 2800) and is estimated at 6.9 million tons. The survey showed continued decreasing trends in hazardous waste generation in the chemical industry. It demonstrated changes in hazardous waste management practices, with decreased use of landfills and increased incineration of the solid wastes that are generated.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Emissions and risks associated with oxyfuel combustion: State of the science and critical data gaps

Oxyfuel combustion is a promising technology that may greatly facilitate carbon capture and sequestration by increasing the relative CO₂ content of the combustion emission stream. However, the potential effect of enhanced oxygen combustion conditions on emissions of criteria and hazardous air pollutants (e.g., acid gases, particulates, metals and organics) is not well studied. It is possible that combustion under oxyfuel conditions could produce emissions posing different risks than those currently being managed by the power industry (e.g., by changing the valence state of metals). The data available for addressing these concerns are quite limited and are typically derived from laboratory-scale or pilot-scale tests. A review of the available data does suggest that oxyfuel combustion may decrease the air emissions of some pollutants (e.g., SO₂, NOx, particulates) whereas data for other pollutants are too limited to draw any conclusions. The oxy-combustion systems that have been proposed to date do not have a conventional “stack” and combustion flue gas is treated in such a way that solid or liquid waste streams are the major outputs. Use of this technology will therefore shift emissions from air to solid or liquid waste streams, but the risk management implications of this potential change have yet to be assessed. Truly useful studies of the potential effects of oxyfuel combustion on power plant emissions will require construction of integrated systems containing a combustion system coupled to a CO₂ processing unit. Sampling and analysis to assess potential emission effects should be an essential part of integrated system tests.

Implications: Oxyfuel combustion may facilitate carbon capture and sequestration by increasing the relative CO₂ content of the combustion emission stream. However, the potential effect of enhanced oxygen combustion conditions on emissions of criteria and hazardous air pollutants has not been well studied. Combustion under oxyfuel conditions could produce emissions posing different risks than those currently being managed by the power industry. Therefore, before moving further with oxyfuel combustion as a new technology, it is appropriate to summarize the current understanding of potential emissions risk and to identify data gaps as priorities for future research.     

Stabilization of Heavy Metal Containing Hazardous Wastes with Byproducts from Advanced Clean Coal Technology Systems

ABSTRACT

The purpose of this investigation was to evaluate the success of residues from advanced Clean Coal Technology (CCT) systems as stabilization agents for heavy metal containing hazardous wastes. In the context examined here, stabilization refers to techniques that reduce the toxicity of a waste by converting the hazardous constituents to a less soluble, mobile, or toxic form.¹ Three advanced CCT byproducts were used: coal waste-fired circulating fluidized bed combustor residue, pressurized fluidized bed combustor residue, and spray drier residue. Seven metal-laden hazardous wastes were treated: three contaminated soils, two air pollution control dusts, wastewater treatment plant sludge, and sandblast waste. Each of the seven hazardous wastes was treated with each of the three CCT byproducts at dosages of 10, 30, and 50% by weight (byproduct:waste). The treatment effectiveness of each mixture was evaluated by the Toxicity Characteristic Leaching Procedure. Of the 63 mixtures evaluated, 21 produced non-hazardous residues. Treatment effectiveness can likely be attributed to mechanisms such as precipitation and encapsulation due to the formation of hydrated calcium silicates and calcium sulfo-alu-minates. Results indicate that these residues have potential beneficial uses to the hazardous waste treatment community, possibly substituting for costly treatment chemicals.     

Automated Economic Analysis Model For Hazardous Waste Minimization

Abstract

The U.S. Army has established a policy of achieving a 50 percent reduction in hazardous waste generation by the end of 1992. To assist the Army in reaching this goal, the Environmental Division of the U.S. Army Construction Engineering Research Laboratory (USACERL) designed the Economic Analysis Model for Hazardous Waste Minimization (EAHWM). The EAHWM was designed to allow the user to evaluate the life cycle costs for various techniques used in hazardous waste minimization and to compare them to the life cycle costs of current operating practices. The program was developed in C language on an IBM compatible PC and is consistent with other pertinent models for performing economic analyses. The potential hierarchical minimization categories used in EAHWM Include source reduction, recovery and/or reuse, and treatment. Although treatment is no longer an acceptable minimization option, its use is widespread and has therefore been addressed in the model. The model allows for economic analysis for minimization of the Army’s six most important hazardous waste streams. These include, solvents, paint stripping wastes, metal plating wastes, industrial waste-sludges, used oils, and batteries and battery electrolytes. The EAHWM also includes a general application which can be used to calculate and compare the life cycle costs for minimization alternatives of any waste stream, hazardous or non-hazardous. The EAHWM has been fully tested and implemented in more than 60 Army installations in the United States.     

Metal catalyzed formation of chlorinated aromatic compounds: a study of the correlation pattern in incinerator fly ash

Chlorinated aromatics are unintentionally formed and released from combustion and other thermal processes involving organic matter and chlorine. The catalytic activity of incinerator fly ash in the low-temperature formation of chlorinated aromatics has been demonstrated in both laboratory experiments and full-scale trials. Copper has been shown to be an effective catalyst, but several other transition metals possess a similar activity. Here results are reported from a series of full-scale combustion trials with different fractions of household and industrial wastes, with waste from forestry as a reference fuel. The composition of elements and chlorinated aromatics in the fly ash was evaluated with principal component analysis and partial least squares regression. The observed correlation pattern indicates that metals other than copper are of equal importance for the catalytic activity. Chromium and nickel are two of these metals, which may contribute to the de novo formation of chlorinated benzenes, phenols, PCDD and PCDF.     

Conversion of chromium-containing solid wastes into value-added products through a plasma-assisted aluminothermic process

Chromium-containing solid wastes have been generated by chemical and leather/tanning industries, and the management and proper disposal of the same wastes have been challenging tasks. A significant fraction of these wastes contains chromium compounds with chromium present in the hexavalent (Cr⁺⁶) form, which is hazardous to human beings, animals, and ecosystems. Since these wastes are discarded largely without proper treatments, soil and groundwater get contaminated and they can cause several health issues to human beings. Conventional methods developed to convert hazardous Cr⁶⁺ to Cr³⁺/Cr metal either generate secondary toxic wastes and unwanted by-products and/or are time-consuming processes. In this work, a plasma-assisted aluminothermic process is developed to convert the toxic waste into non-toxic products. The waste was mixed with aluminium powder and subjected to transferred arc plasma treatment in a controlled air atmosphere. Chemical analysis and Cr leachability studies of the waste material prior to plasma treatment have shown that it is highly toxic. Analysis of the products obtained from the plasma treatment showed that Cr and Fe present in the waste could be recovered as a metallic mixture as well as oxide slag, which were found to be non-toxic. Easy separation of the metallic fraction and the slag from the treated product is one of the merits of this process. Besides converting chromium-containing toxic waste to non-toxic materials, the process is rapid and recovers the metals from the waste completely.

     

Hazardous Waste Minimization: Part VI Waste Minimization in the Foundry Industry

The foundry industry is a major consumer of waste materials (scrap). Unfortunately, the recycling of these waste materials can result in the generation of hazardous wastes that must be properly managed at a significant cost. This article focuses on two waste streams in the foundry industry; calcium carbide desulfurization slag and melt emission control residuals. The author presents an overview of how foundries have evaluated different waste management options with the ultimate goal of minimizing the generation of hazardous waste.     

Flow rates and compositions of incinerated waste streams in the United States.

The quantity and composition of RCRA hazardous wastes incinerated during 1986 were examined using the National Hazardous Waste Survey. This Survey, collected for U.S. EPA by the Research Triangle Institute, is the most extensive examination of hazardous waste generation and management available. The survey data show that although a wide variety of hazardous wastes were treated by incineration, more than 75 percent of incinerated waste streams were from chemical manufacturing. The survey data also show that more than 90 percent of the incinerated wastes were treated by incinerators located at the facility generating the waste. Despite the predominance of a single industrial sector in generating incinerated hazardous wastes, the compositional profile of the wastes is far from uniform. To illustrate this variability, the metals and chlorine content of the wastes are reported along with the sources of the metal and chlorine loadings.     

Treatment Technologies For Hazardous Wastes: Part IV A Review of Alternative Treatment Processes for Metal Bearing Hazardous Waste Streams

The U.S. Congress and the U.S. Environmental Protection Agency believe that treatment and recovery techniques should be given maximum priority when considering methods for managing the nation's generated hazardous waste. A prohibition for the disposal of certain categories of hazardous wastes either directly onto or into the land without being treated to an accepted degree prior to such disposal practice has been promulgated.¹ Wastes containing toxic metals and cyanide complexes have been selected as a group to be restricted. Due to the high generation rate associated with this category, a large capacity of waste treatment processing will be required. Existing and emerging treatment alternatives which are or have the potential to be employed for waste treatment of metal bearing wastes are presented in this paper.     

Performance of High-temperature Slagging Rotary Kiln Incinerator

A high-temperature, slagging rotary kiln hazardous waste incineration system with modern combustion, heat recovery and air pollution control equipment was put in operation at PPG Coating and Resin Plant in Circleville, Ohio in the latter part of 1987. New design solutions contributed to the overall high performance of the system. The system employs European and American feed, combustion, heat recovery and stack emission control technologies. Performance of the system is analyzed in detail covering topics such as feed methods, equipment selection, destruction and removal efficiencies, fate of the metals, and financial information.     

Practical Incinerator Implications

This paper discusses a number of results obtained from a hazardous waste flat flame combustion study with implications to full scale incinerators. The results demonstrate that it is possible to obtain DREs of up to 99.95 percent firing mixtures of CH₂Cl₂/CH₄ and air in such a facility. These results are significant since residence times are at the millisecond level. The paper presents DRE results obtained with this CH₂Cl₂ flat flame system when systematically varying the chlorine loading and equivalence ratio within the flames. Additionally, a PIC DRE is defined as an alternative approach to measure total stack emissions. PIC DRE results are presented for systematic variation of chlorine loading and equivalence ratio. Based upon the data of the paper, a suggested two-stage incineration process is presented which may be both economically advantageous and result in less total PIC emissions as compared with conventional incinerators for certain wastes. The data of this work further indicate that it is kinetically possible to obtain high DREs with corresponding high CO levels for select wastes. Finally, an interpretation of the data suggests that, for a class of liquid wastes, it may be beneficial to vaporize the waste and premix it with gaseous fuel and oxidizer streams, thereby avoiding the need to atomize the waste.