Products of incomplete combustion

RCRA incinerator regulations include adrninistrative as weU as performance standards. Administrative standards include procedures for waste analysis, inspection of equipment, monitoring, and facihty security. Steps needed to meet adrninistrative standards are outlined ia the permit apphcation performance standards are demonstrated during a trial bum. Trial bum operating conditions are included in the permit to assure ongoing compliance with the performance standards. Performance standards include destmction and removal efficiency (DRE), particulate emissions limits, products of incomplete combustion emission limits, metal emission limits, and HCl and Cl emission limits (see Exhaust CONTROL, INDUSTRIAL). 

Products of Incomplete Combustion Emission Limits. Products of iacomplete combustion typically are not directly measured duting the trial bum. Instead, levels of carbon monoxide (qv) emissions are used as an iadication of combustion efficiency. High combustion efficiencies are assumed to result ia acceptable levels of products of incomplete combustion. If carbon monoxide emissions are measured at less than 100 ppmv dry basis, the standard is met. However, if emissions are greater than 100 ppmv, no more than 20 ppmv of total hydrocarbons (qv) are allowed at the iaciaerator stack duting the trial bum. 

Chemical Reaction Measurements. Experimental studies of incineration kinetics have been described (37—39), where the waste species is generally introduced as a gas in a large excess of oxidant so that the oxidant concentration is constant, and the heat of reaction is negligible compared to the heat flux required to maintain the reacting mixture at temperature. The reaction is conducted in an externally heated reactor so that the temperature can be controlled to a known value and both oxidant concentration and temperature can be easily varied. The experimental reactor is generally a long tube of small diameter so that the residence time is well defined and axial dispersion may be neglected as a source of variation. Off-gas analysis is used to track both the disappearance of the feed material and the appearance and disappearance of any products of incomplete combustion. 

The equiHbrium approach should not be used for species that are highly sensitive to variations in residence time, oxidant concentration, or temperature, or for species which clearly do not reach equiHbrium. There are at least three classes of compounds that cannot be estimated weU by assuming equiHbrium CO, products of incomplete combustion (PlCs), and NO. Under most incineration conditions, chemical equiHbrium results in virtually no CO or PlCs, as required by regulations. Thus success depends on achieving a nearly complete approach to equiHbrium. Calculations depend on detailed knowledge of the reaction network, its kinetics, the mixing patterns, and the temperature, oxidant, and velocity profiles. 

Combustion. The burning of soHd, Hquid, and gaseous fuels as a source of energy is very common. Using sufficient and reHable combustion controls, this process seldom causes serious problems. However, some combustion processes are deHberately carried out with an inadequate oxygen supply in order to obtain products of incomplete combustion. Explosive mixtures sometimes occur, and then flashback is a serious problem. 

Occurrence. Carbon monoxide is a product of incomplete combustion and is not likely to result where a flame bums in an abundant air supply, yet may result when a flame touches a cooler surface than the ignition temperature of the gas. Gas or coal heaters in the home and gas space heaters in industry have been frequent sources of carbon monoxide poisoning when not provided with effective vents. Gas heaters, though properly adjusted when installed, may become hazardous sources of carbon monoxide if maintained improperly. Automobile exhaust gas is perhaps the most familiar source of carbon monoxide exposure. The manufacture and use of synthesis gas, calcium carbide manufacture, distillation of coal or wood, combustion operations, heat treatment of metals, fire fighting, mining, and cigarette smoking represent additional sources of carbon monoxide exposure (105—107). 

One of the reasons the tribes of early history were nomadic was to move periodically away from the stench of the animal, vegetable, and human wastes they generated. When the tribesmen learned to use fire, they used it for millennia in a way that filled the air inside their living quarters with the products of incomplete combustion. Examples of this can still be seen today in some of fhe more primitive parts of the world. After its invention, the chimney removed the combustion products and cooking smells from the living quarters, but for centuries the open fire in the fireplace caused its emission to be smoky. In ad 61 the Roman philosopher Seneca reported thus on conditions in Rome ... 

Measures such as improved process design, operation, maintenance, housekeeping, and other management practices can reduce emissions. By improving combustion efficiency, the amount of products of incomplete combustion (PlCs), a component of particulate matter, can be significantly reduced. Proper fuel-firing practices and... 

Air emissions for processes with few controls may be of the order of 30 kilograms lead or zinc per metric ton (kg/t) of lead or zinc produced. The presence of metals in vapor form is dependent on temperature. Leaching processes will generate acid vapors, while refining processes result in products of incomplete combustion (PICs). Emissions of arsine, chlorine, and hydrogen chloride vapors and acid mists are associated with electrorefining. 

In general, the environmental consequences resulting from emissions generated by the combustion of treated wood and the chemicals used to treat them are not well understood. Combustion of the materials involved in the incident unquestionably produced hazardous products of incomplete combustion emissions (e.g., dioxins and furans). 

The characterization of PIC (products of incomplete combustion) from the combustion of wood treated with pentachlorophenol (penta) is more widely documented in the open literature than creosote alone. However, both products are similar in chemical composition and likely result in comparable forms and concentrations of PIC. Literature reported studies on the combustion of these chemicals and wood treated by them, and the PIC generated are based upon optimal conditions. Optimal conditions are defined as those in which the fuel burns at the designed heat release rate with nominally 160% excess air and a low level (< 100 ppm) of carbon monoxide (CO) emissions in combustion (flue) gases. 

Smoke - Smoke constitutes fine, solid, gasbome matters that are products of incomplete combustion of organics (wood, coal, tobacco). Smoke particles are extremely small, ranging in size from less than 0.01 /im to 1 /im. 

The subsequent fate of the assimilated carbon depends on which biomass constituent the atom enters. Leaves, twigs, and the like enter litterfall, and decompose and recycle the carbon to the atmosphere within a few years, whereas carbon in stemwood has a turnover time counted in decades. In a steady-state ecosystem the net primary production is balanced by the total heterotrophic respiration plus other outputs. Non-respiratory outputs to be considered are fires and transport of organic material to the oceans. Fires mobilize about 5 Pg C/yr (Baes et ai, 1976 Crutzen and Andreae, 1990), most of which is converted to CO2. Since bacterial het-erotrophs are unable to oxidize elemental carbon, the production rate of pyroligneous graphite, a product of incomplete combustion (like forest fires), is an interesting quantity to assess. The inability of the biota to degrade elemental carbon puts carbon into a reservoir that is effectively isolated from the atmosphere and oceans. Seiler and Crutzen (1980) estimate the production rate of graphite to be 1 Pg C/yr. 

Mere destruction of the original hazardous material is not, however, an adequate measure of the performance of an incinerator. Products of incomplete combustion can be as toxic as, or even more toxic than, the materials from which they evolve. Indeed, highly mutagenic PAHs are readily generated along with soot in fuel-rich regions of most hydrocarbon flames. Formation of dioxins in the combustion of chlorinated hydrocarbons has also been reported. We need to understand the entire sequence of reactions involved in incineration in order to assess the effectiveness and risks of hazardous waste incineration. 

Both classes of hydrocarbon occur naturally, notably in oil and coal deposits. Aromatic compounds are also products of incomplete combustion of organic compounds, and are released into the environment both by human activities, and by certain natural events, for example, forest tires and volcanic activity. 

The products of incomplete combustion may be associated with particulate matter before their discharge into the atmosphere, and these may ultimately enter the aquatic and terrestrial environments in the form of precipitation and dry deposition. It is therefore essential to ensure total destruction of the contaminants, generally by raising the temperature. The spectrum of compounds that have been examined is quite extensive, and several of them are produced by reactions between hydrocarbons and inorganic sulfur or nitrogen constituents of air. Some illustrative examples involving other types of reaction include the following ... 

In electrocatalysis, the activated carbons, glassy carbon, and carbon black are the transitional forms used. Carbon black is the product of incomplete combustion or decomposition of organic compounds. The shape of its particles is close to spherical. They contain several carbon atom lattice fragments arranged without order. Various types of carbon black serve as substrates for metal catalysts, the properties of the carbon blacks themselves having a strong elfect on the catalytic activity of the combined catalysts thus obtained. 

The stable gases produced by incineration are primarily carbon dioxide and water. Depending on waste composition, however, small quantities of carbon monoxide, nitrogen oxides, HC1, and other gases may form. Also, if combustion is not complete, compounds known as products of incomplete combustion (PICs) may be emitted. RCRA regulations control the amount of HC1 released from the APCD. 

Notification of intent to comply Product of incomplete combustion Particulate matter... 

Dragoescu, C., Friedlander, S. (1989) Dynamics of the aerosol products of incomplete combustion in urban atmospheres. Aerosol... 

In our tests, the furnace was occasionally deficient of oxygen. When oxygen level went to zero, a significant amount of CO was produced as well as visible and sooty smoke. These are indications of incomplete combustion. The only product of incomplete combustion monitored was CO. Incomplete combustion products other than CO were not accounted for. 

Smoke abatement from the thermal reduction batch processor (TRBP) smoking rooms and the measurement and management of carbon monoxide and other products of incomplete combustion generated in these rooms. (These processes were not adequately addressed in the EDP.)... 

PCDD/F and other chlorinated hydrocarbons observed as micropollutants in incineration plants are products of incomplete combustion like other products such as carbon monoxide, polycyclic aromatic hydrocarbons (PAH), and soot. The thermodynamically stable oxidation products of any organic material formed by more than 99% are carbon dioxide, water, and HCl. Traces of PCDD/F are formed in the combustion of any organic material in the presence of small amounts of inorganic and organic chlorine present in the fuel municipal waste contains about 0.8% of chlorine. PCDD/F formation has been called the inherent property of fire. Many investigations have shown that PCDD/Fs are not formed in the hot zones of flames of incinerators at about 1000°C, but in the postcombustion zone in a temperature range between 300 and 400°C. Fly ash particles play an important role in that they act as catalysts for the heterogeneous formation of PCDD/Fs on the surface of this matrix. Two different theories have been deduced from laboratory experiments for the formation pathways of PCCD/F ... 

Biomass has some advantageous chemical properties for use in current energy conversion systems. Compared to other carbon-based fuels, it has low ash content and high reactivity. Biomass combustion is a series of chemical reactions by which carbon is oxidized to carbon dioxide, and hydrogen is oxidized to water. Oxygen deficiency leads to incomplete combustion and the formation of many products of incomplete combustion. Excess air cools the system. The air requirements depend on the chemical and physical characteristics of the fuel. The combustion of the biomass relates to the fuel bum rate, the combustion products, the required excess air for complete combustion, and the fire temperatures. 

There are two interesting molecules that are derived from carbon and oxygen alone. Earlier, we encountered carbon dioxide, CO2, as a constituent of our atmosphere, a product of the combustion of fossil fuels, and a major contributor to global warming. An even simpler molecule is carbon monoxide, CO, a toxic gas and a minor product of incomplete combustion of fossil fuels. 

Because cement kilns are so good at destroying organic chemical wastes, emissions of dioxins - or any other type of products of incomplete combustion (PIC) - are so low they pose no danger to the environment. In the case where some of the hazardous waste fuels used contain toxic dioxin, the cement kiln temperatures of 1650°F will destroy dioxins in less than one second. Because cement kilns operate at much higher temperatures (at least 2450°F), and because the burning wastes have an average residence time in the kiln of at least two seconds, any dioxins are destroyed. However, dioxin waste is never accepted by Southdown for use in its cement kilns. 

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