Industrial processes and emission of pollutants - PlasTEP · Prevention and control of industrial emissions Industrial activities ... The main technologies applied for chlor-

Part-financed by the European Union (European Regional Development Fund

Industrial processes and emission of pollutants

Jelena Pubule, RTU researcher

Dr.Hab. sc. ing. Dagnija Blumberga

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Prevention and control of industrial emissions

Industrial activities play an important role in the economicwell-being of Europe contributing to sustainable growth. However,industrial activities also have a significant impact on theenvironment.

The largest industrial installations account for a considerable shareof total emissions of key atmospheric pollutants and also haveother important environmental impacts, including emissions towater and soil, generation of waste and the use of energy.


Emissions from industrial installations

Emissions from industrial installations have therefore been subjectto EU-wide legislation for some time and currently the followingmain pieces of legislation apply in this field:

• The IPPC Directive concerning integrated pollution prevention and control;

• Sectoral directives, which lay down specific minimum requirements.

• The Regulation on the European Pollutant Release and Transfer Register (E-PRTR).

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IPPC Directive

The IPPC Directive concerning integrated pollution prevention andcontrol, which sets out the main principles for the permitting andcontrol of installations based on an integrated approach and theapplication of best available techniques (BAT) which are the mosteffective techniques to achieve a high level of environmentalprotection, taking into account the costs and benefits.

Industrial processes and emission of pollutants 3

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European Pollutant Releaseand Transfer Register

The Regulation on the E-PRTR, which makes accessible to thepublic detailed information on the emissions and the off-sitetransfers of pollutants and waste from approx. 24 000 industrialfacilities.


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CO2 emissions in EU 27, 2009


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CO2 emissions by source

Vides aizsardzības un siltuma sistēmu institūts 6

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Industrial facilities. Emissions to the air

• energy ;

• production and processing of metals;

• mineral industry;

• chemical industry;

• waste and waste water management;

• paper and wood production and processing;

• intensive livestock production and aquaculture;

• animal and vegetable products from the food and beverage sector, and;

• other activities.


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Cement, Lime and Magnesium Oxide Manufacturing Industries

Cement is a basic material used for building and civil engineeringconstruction. The production of cement in the European Unionstood at 267.5 million tonnes in 2006, equivalent to about 10.5 %of world production.


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The clinker burning process is the most important part of the process in terms of the key environmental issues for cement manufacture: energy use and emissions to air.

The key polluting substances emitted to air are dust, nitrogen oxides andsulphur dioxide. Carbon oxides, polychlorinated dibenzo-p-dioxins anddibenzofurans, total organic carbon, metals, hydrogen chloride andhydrogen fluoride are emitted as well. The type and quantity of airpollution depend on different parameters, e.g. inputs (the raw materialsand fuels used) and the type of process applied.


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To produce 1 tonne of clinker, the typical average consumption of rawmaterials in the EU is 1.52 tonnes. Most of the balance is lost from theprocess as carbon dioxide emissions to air in the calcination reaction(CaCO3 H CaO + CO2).


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Ceramic Manufacturing Industry

Generally the term ‘ceramics’ (ceramic products) is used for inorganic materials (with possibly some organic content), made up of non-metallic compounds and made permanent by a firing process. In addition to clay based materials, today ceramics include a multitude of products with a small fraction of clay or none at all. Ceramics can be glazed or unglazed, porous or vitrified.


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Ceramic Manufacturing Industry

Depending on the specific production processes, plants manufacturingceramic products cause emissions to be released into air, water and land(waste). Additionally, the environment can be affected by noise andunpleasant smells. The type and quantity of air pollution, wastes andwaste water depend on different parameters.

These parameters are, e.g. the raw materials used, the auxiliary agents employed, the fuels used and the production methods:emissions to air: particulate matter/dust, soot, gaseous emissions(carbon oxides, nitrogen oxides, sulphur oxides, inorganic fluorine andchlorine compounds, organic compounds and heavy metals) can arisefrom the manufacture of ceramic products.


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Chlor-alkali Manufacturing Industry

The chlor-alkali industry is the industry that produces chlorine (Cl2) andalkali, sodium hydroxide (NaOH) or potassium hydroxide (KOH), byelectrolysis of a salt solution. The main technologies applied for chlor-alkali production are mercury, diaphragm and membrane cellelectrolysis, mainly using sodium chloride (NaCl) as feed or to a lesserextent using potassium chloride (KCl) for the production of potassiumhydroxide.


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Chlor-alkali Manufacturing Industry

The main pollutant outputs which are common to all three electrolytic processes are chlorine gas emissions to air, free oxidants to water, spent acids, cooling agents, and impurities removed from the input salt or brine.


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Chemical Sector

Discharges to air and water are the main environmental impacts caused by releases from chemical installations.

Waste gas emissions appear as:

• ducted emissions, which are the only emissions that can be treated

• diffuse emissions

• fugitive emissions.


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Chemical Sector

The main air pollutants are:

• VOCs

• sulphur compounds (SO2, SO3, H2S, CS2, COS)

• nitrogen compounds (NOx, N2O, NH3, HCN)

• halogen compounds (Cl2, Br2, HF, HCl, HBr)

• incomplete combustion compounds (CO, CxHy)

• particulate matter.


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Ferrous Metals Processing Industry

The hot and cold forming part of the ferrous metal processing sectorcomprises different manufacturing methods, such as hot rolling, coldrolling and drawing of steel. A great variety of semi-finished andfinished products with different lines of production is manufactured.

Products are: hot and cold rolled flats, hot rolled long products, drawn long products, tubes and wire.


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Ferrous Metals Processing Industry

The main environmental issues of hot rolling are emissions to air,especially NOx and SOx; the energy consumption of furnaces; (fugitive)dust emissions from product handling, rolling or mechanical surfacetreatment; oil- and solid-containing effluents and oil-containing wastes.

The main environmental issues of cold rolling are: acidic wastes andwaste water; degreaser fume, acidic and oil mist emissions to air; oil-containing wastes and waste water; dust, e.g. From descaling anddecoiling; NOx from mixed acid pickling and combustion gases fromfurnace firing.


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Iron and Steel Production

The iron and steel industry is a highly material and energy intensiveindustry. More than half of the mass input becomes outputs in the formof off-gases and solid wastes/by-products. The most relevant emissionsare those to air.


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Iron and Steel Production

Those from sinter plants dominate the overall emissions for most of the pollutants. Although big efforts have been made to reduce emissions, the contribution of the sector to the total emissions to air in the EU is considerable for a number of pollutants, especially for some heavy metals and PCDD/F. The rate of reuse and recycling of solid wastes/by-products has been increased dramatically in the past but considerable amounts are still disposed to landfills.


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Non-ferrous Metals Industries

At least 42 non-ferrous metals plus ferro alloys and carbon and graphite are produced in EU and are used in a variety of applications in the metallurgical, chemical, construction, transport and electricity generation/transmission industries.


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Non-ferrous Metals Industries

The main environmental issues for the production of most non-ferrous metals from primary raw materials are the potential emission to air of dust and metals/metal compounds and of sulphur dioxide to if roasting and smelting sulphide concentrates or using sulphur-containing fuels orother materials.

The capture of sulphur and its conversion or removal is therefore an important factor in the production of non-ferrous metals. The pyrometallurgical processes are potential sources of dust and metals from furnaces, reactors and the transfer of molten metal.


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Glass Manufacturing Industry

All of the sectors within the glass industry involve the use of powdered,granular or dusty raw materials. The storage and handling of thesematerials represents a significant potential for dust emissions.

The major environmental challenges for the glass industry are emissionsto air and energy consumption.


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Glass Manufacturing Industry

Glass making is a high temperature, energy intensive activity, resulting inthe emission of products of combustion and the high temperatureoxidation of atmospheric nitrogen; i.e. sulphur dioxide, carbon dioxide,and oxides of nitrogen.

Furnace emissions also contain dust and lower levels of metals. It isestimated that in 1997 the glass industry emissions to air consisted of:9000 tonnes of dust; 103500 tonnes of NOx; 91500 tonnes of SOx; and 22million tonnes of CO2 (including electrical generation). This amounted toaround of 0.7 % of total EU emissions of these substances. Total energyconsumption by the glass industry was approximately 265 PJ.


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Large Combustion Plants

In the European Union, all available types of energy sources areused for electric and thermal power generation. National fuelresources such as the local or national availability of coal, lignite,biomass, peat, oil and natural gas, largely influence the choice offuel used for energy generation in each EU Member State.


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Large Combustion Plants

The most important emissions to air from the combustion of fossil fuels are SO2, NOX, CO,

particulate matter (PM10) and

greenhouse gases, such as N2O and CO2.

Other substances such as heavy metals,

halide compounds, and

dioxins are emitted in smaller quantities.


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Large Volume Inorganic Chemicals - Ammonia, Acids and Fertilizers Industries

Fertiliser production currently accounts for about 2 – 3 % of the totalglobal energy consumption.

The main pollutants emitted to air are NOx, SO2, HF, NH3 and dust, whichare, depending on the particular source, emitted at high volume flows. Inthe production of HNO3, considerable amounts of the greenhouse gasN2O are generated.


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Large Volume Inorganic Chemicals - Solids and Others Industry

The EU chemical industry has a growth rate about 50 % higher than that of the EU economy, and when the growth of the EU chemical industry (3.1 %) is compared by sector, the production growth of basic inorganic chemicals is the least dynamic (0.2 %).

The share of the EU in global production of chemicals is dropping, the dynamism of the chemical industry derives not only from its growth but also from rapid technological change hat is one of the industry’s outstanding features.


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Surface Treatment Using Organic Solvents

This is not a homogenous sector and covers several industries, withinstallation sizes ranging from SME to multinational.

About 4.5 million tonnes of solvents a year are sold for use in Europe, 27% (2003) of this is used in the paint and coatings industries, a decreasefrom 47 % (1998) due to increased use of water-based, powdertechnologies and other low-solvent technologies.

Printing ink formulations use about 7 % and adhesives about 4 %.


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Surface Treatment Using Organic Solvents

The main environmental issues relate to the emission of solvents to air,water and groundwaters, and soil. Energy usage is also important, as areparticulate emissions to air, waste minimization and management(including reducing raw material consumption by increased applicationefficiency) and site condition on cessation of activities.


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Mineral Oil and Gas Refineries

The mineral oil and gas refinery industry is an important and strategicindustry. Mineral oil refineries alone provide 42% of EU energyrequirements and 95% of the fuels required for transport. About 100mineral oil refineries have been identified in EU, Switzerland and Norwayand together they process around 700 million tonnes per year.Installations are well spread around the European geography, generallylocated near the coast.


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Mineral Oil and Gas Refineries

Refinery installations are typically big and fully integrated. Refineries areindustrial sites that manage huge amounts of raw materials and productsand they are also intensive consumers of energy and water.

In their storage and refining processes, refineries generate emissions tothe atmosphere, to the water and to the soil, to the extent thatenvironmental management has become a major factor for refineries.

Oxides of carbon, nitrogen and sulphur, particulates mainly generatedfrom combustion processes, and volatile organic carbons are the main airpollutants generated by sector.


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Intensive Rearing of Poultry and Pigs

Early seventies, poultry and pig production were only part of the activitiesof a mixed farm, where crops were grown and different animal specieswere kept. Feed was grown on the farm or purchased locally and residuesof the animal were returned to the land as fertiliser.

Only a very small number of this type of farm may still exist in the EU,because increasing market demands, the development of genetic materialand farming equipment and the availability of relatively cheap feed hasencouraged farmers to specialise. As a consequence animal numbers andfarm sizes have increased and intensive livestock farming began.


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Intensive Rearing of Poultry and Pigs

Environmental problems: acidification (NH3, SO2, NOx), eutrophication(N, P), local disturbance (odour, noise) and diffuse spreading of heavymetals and pesticides.


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Tanning of Hides and Skins

The EU is the world's largest supplier of leather in the international marketplace. Italy is the major country in Europe in terms of establishments, employment, production and turnover. It accounts for 15 % of the world's cattle and calf leather production and 65 % of EC production.


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Tanning of Hides and Skins

Due to the wide versatility of tanneries, both in terms of the types ofhides and skins used and the range of products manufactured, thereported emission and consumption levels are generally indicative. Theyserve to indicate the ranges of emission and consumption levels that canbe seen in a wide range of tanneries.

The main releases to air are due to the dry-finishing processes, althoughgaseous emissions may also arise in all other parts of the tannery.


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Textiles Industry

The textile industry is one of the longest and most complicatedindustrial chains in manufacturing industry. It is a fragmented andheterogeneous sector dominated by a majority of Small and MediumEnterprises, with a demand largely driven by three main end-uses:clothing, home furnishing and industrial use.

Air emissions are usually collected at their point of origin. Because they have been controlled for quite a long time in different countries, there are good historical data on air emissions from specific processes.


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Waste Incineration

Three main thermal treatment techniques:

• incineration • pyrolysis • gasification


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Waste Incineration

Emissions to air have long been the focus of attention for waste incineration plants. Significant advances in technologies for the cleaning of flue-gases in particular have lead to major reductions in the emissions to air.

However, the control of emissions to air remains an important issue for the sector.

As the entire incineration process is usually under slightly negative pressure (because of the common inclusion of an induced draught extraction fan), routine emissions to air generally take place exclusively from the stack.


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Emissions from Storage

Important emissions to air from the storage of liquid and liquefied gasesduring normal operation are differentiated as follows:

• emissions during entry and evacuation i.e. transferring substances inand out of storage (filling and emptying)

• emissions during tank breathing, i.e. emissions due to temperatureincreases resulting in vapour space expansions and subsequentemissions

• fugitive emissions from flange seals, fittings andpumps

• emissions during sampling

• emissions from cleaning operations.


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Emissions from Storage

The following categories of emissions from dusty bulk materials may be distinguished:

• emissions during loading of the material

• emissions during discharge of the material

• emissions during conveyance of the material

• emissions during storage of the material.



Environmental Technologies

Solutions to avoid air pollution:

●Cleaner production – to avoid and prevent causes and reasons of air pollution;

●End of pipe solutions – fights with effects and consequences;

●Zero emissions


Cleaner production


Technological solutions – to avoid pollution

Best available technologies (BAT)

Operation and management optimization

● EMAS

● ISO 14001

● ISO 16001

Specific technological solutions (particularly NOx) to prevent arising of air pollutants


End of pipe solutions


Engineering solutions

Best Available Technologies

Gas abatement equipment

●Absorption processes

●Adsorption processes

●Catalytic processes

●Plasma technologies

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Adsorption

The principle of adsorption is based on the interaction of gases and solids.

With adsorption chilling, the molecular interaction between the solid and the gas allow the gas to be adsorbed into the solid.


Adsorption

Adsorption is present in many natural physical, biological, and chemical systems, and is widely used in industrial applications such as:

●activated charcoal capturing and using waste heat to provide cold water for air conditioning and other process requirements,

●synthetic resins increase storage capacity of carbide-derived carbons for tunable nonporous carbon, and water purification.

Adsorption, ion exchange, and chromatography are sorption processes in which certain adsorbates are selectively transferred from the fluid phase to the surface of insoluble, rigid particles suspended in a vessel or packed in a column.


Industrial adsorbents

Most industrial adsorbents fall into one of three classes:

●Oxygen-containing compounds – Are typically hydrophilic and polar, including materials such as silica gel and zeolites.

●Carbon-based compounds – Are typically hydrophobic and non-polar, including materials such as activated carbon and graphite.

●Polymer-based compounds - Are polar or non-polar functional groups in a porous polymer matrix.

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Absorption


Absorbers

In a wet scrubber, the polluted gas stream is brought into contactwith the scrubbing liquid, by spraying it with the liquid, by forcing itthrough a pool of liquid, or by some other contact method, so as toremove the pollutants.

The design of wet scrubbers or any air pollution control devicedepends on the industrial process conditions and the nature of the airpollutants involved.

Inlet gas characteristics and dust properties (if particles are present)are of primary importance. Scrubbers can be designed to collectparticulate matter and/or gaseous pollutants.

Wet scrubbers remove pollutant gases by dissolving or absorbingthem into the liquid.


Absorption. SOx control

SO2 is an acid gas and thus the typical sorbent slurries or other materials used to remove the SO2 from the flue gases are alkaline. The reaction taking place in wet scrubbing using a CaCO3 (limestone) slurry produces CaSO3 (calcium sulfite) and can be expressed as:

●CaCO3 (solid) + SO2 (gas) → CaSO3 (solid) + CO2 (gas)

When wet scrubbing with a Ca(OH)2 (lime) slurry, the reaction also produces CaSO3 (calcium sulfite) and can be expressed as:

●Ca(OH)2 (solid) + SO2 (gas) → CaSO3 (solid) + H2O (liquid)


Catalytic converter

A catalytic converter provides an environment for a chemical reduction wherein toxic combustion by-products are converted to less-toxic substances.

Reduction of nitrogen oxides to nitrogen and oxygen:

2NOx → O2 + N2

Oxidation of carbon monoxide to carbon dioxide:

2CO + O2 → 2CO2

Oxidation of unburnt hydrocardons (HC) to carbon dioxide and water:

CxH2x+2 + [(3x+1)/2]O2 → xCO2 + (x+1)H2O

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Catalytic converter

A catalytic converter is a device used to reduce the toxicity of emissionsfrom an internal combustion engine.

First widely introduced on cars in the market for the 1975 model yearto comply with tightening EPA regulations on auto exhaust,catalytic converters are still most commonly used in motor vehicleexhaust systems.

Catalytic converters are also used on generator sets, forklifts, miningequipment, trucks, buses, trains, airplanes and other engine-equippedmachines.

A catalytic converter provides an environment for a chemical reactionwherein toxic combustion by-products are converted to less-toxicsubstances.


SOx control

Additives to combustion process

Absorption process

Catalityc process

Plasma technologies


SOx control. Absorption

When wet scrubbing with a Mg(OH)2 (magnesium hydroxide) slurry, the reactionproduces MgSO3 (magnesium sulfite) and can be expressed as:

●Mg(OH)2 (solid) + SO2 (gas) → MgSO3 (solid) + H2O (liquid)

In some designs, the CaSO3 (calcium sulfite) is further oxidized to producemarketable CaSO4 · 2H2O (gypsum). This technique is also known as forcedoxidation:

●CaSO3 (solid) + H2O (liquid) + ½O2 (gas) → CaSO4 (solid) + H2O

A natural alkaline usable to absorb SO2 is seawater. The SO2 is absorbed in thewater, and when oxygen is added reacts to form sulfate ions SO4

- - and free H+.The surplus of H+ is offset by the carbonates in seawater pushing the carbonateequilibrium to release CO2 gas:

●SO2 (gas) + H2O + ½O2 (gas)→ SO42- (solid) + 2H+

●HCO32- + H+ → H2O + CO2 (gas)


NOx Control

Cleaner technology

Low NOx burners

Exhaust gas recirculation

End of pipe solutions

Selective catalytic reduction (SCR)

Selective non-catalytic reduction (SNCR)

NOx scrubbers

Catalytic converter (also for VOC control)

Plasma technologies

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VOC abatement

Adsorption systems, such as activated carbon

Flares

Thermal oxidizers

Catalytic oxidizers

Biofilters

Absorption (scrubbing)

Cryogenic condensers

Vapor recovery system

Plasma technologies


VOC Emission from Offshore Crude Oil Loading and Storage

Three alternative methods has so far been developed and tested to reduce NMVOC emissions during loading operations:

●Absorption of NMVOC into the crude during loading;

●Liquefaction and storage of NMVOC and use as fuel;

●Sequential transfers of tank atmospheres during loading and discharge.

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Gas flare


Biofilters

When applied to air filtration and purification, biofilters usemicroorganisms to remove air pollution.

The air flows through a packed bed and the pollutant transfers into a thinbiofilter on the surface of the packing material.

Microorganisms, including bacteria and fungi are immobilized in thebiofilter and degrade the pollutant. Trickling filters and bioscrubbers relyon a biofilter and the bacterial action in their recirculating waters.


Biofilters

Very large airflows may be treated and although a large area (footprint)has typically been required -- a large biofilter may occupy as much ormore land than a football field -- this has been one of the principaldrawbacks of the technology.

Engineered biofilters, designed and built since the early 1990s, haveprovided significant footprint reductions over the conventional flat-bed,organic media type.


Biofilters

The technology finds greatest application in treating malodorouscompounds and water-soluble volatile organic compounds (VOCs).

Industries employing the technology include food and animal products,off-gas from wastewater treatment facilities, pharmaceuticals, woodproducts manufacturing, paint and coatings application andmanufacturing and resin manufacturing and application, etc.

Compounds treated are typically mixed VOCs and various sulfurcompounds, including hydrogen sulfide.


Thermal Oxidizers

Thermal Oxidizers are typically used to destroy Hazardous Air Pollutants(HAPs) and Volatile Organic Compounds (VOCs) from industrial airstreams.

These pollutants are generally hyrdocarbon based and when destroyedvia thermal combustion they are chemically changed to form CO2 andH2O.


Thermal Oxidizers


Vapour recovery

Vapor recovery is the process of recovering the vapors of gasoline or other fuels, so that they do not escape into the atmosphere. This is often done (or required by law) at filling stations, in order to reduce noxious and potentially explosive fumes and pollution.

The negative pressure created in the (underground) tank by the withdrawal is usually used to pull in the vapors.

They are drawn-in through holes in the side of the nozzle and travel through special hoses which have a return path.

Documents

Industrial processes and emission of pollutants - PlasTEP · Prevention and control of industrial emissions Industrial activities ... The main technologies applied for chlor-