es Tn Chemical Hendin Reaching Prners Hyon Ronde Ho, bn a baeSomamowtel rp adm NATURE AND SOURCES OF KRAFT EMISSIONS 2.1 GASEOUS EMISSIONS Gaseous emissions from a keat mill orginate ftom different sources and can have very sitferent characteristics. Ths is a major consideration when selecting a control technology The major gaseous emissions from kratt pulp mill sources are the malodorous reduced sulphur compounds such as hydrogen sulphide (4,8), methyl mercaptan (CH,SH) imethy! sulphide (CH,SCH). and dimethyl disulphide (CH,5,CHy). ones of supnur (50) and oxides of nitrogen (NO). In addition, chlorine (C,) and chlorine dioxide (CIO,) can also be emitted from bleach tank vents and sewers, 2.1.1 Total reduced sulphur gases (TRS) TAS is not a single gas but a term covering a mixture of sulphur containing gases consisting of hydrogen sulphide (H,S), methyt mercaptan (CH,SH). dimethyl sulphide (CH,SCH). and dimethy! disulphide (CH,S,CH,). Both H,S and the organic sulphides are extremely odorous and have very low odour threshold levels (between 1 and 10 parts per billion by volume (ppbv). This makes it very dificult o eliminate all odour from kraft pulp‘mills and itis why odour control is one of the most challenging air pollution problems in a raft pulp mil ‘The major TRS enission sources in the mill include the digester blow and relie! gases, the vacuum washer hood and seal tank vents, the mulple-etfect evaporatior hotwell vents, the chemical recovery furnace flue gases following direct contact evaporation, the. ‘melt dissolving tanks, the slaker vents, the black liquor oxidation tank, the lime kiln and waste water treatment operations. These are summarized in Table | {nthe pulping area, the digester blow gas is the main TRS source, It is a low volume, high concentration source (upwards of 100,000 parts per million by volume (ppmw) are possible if uncontrolled). Knoting and brownstock washing isthe next major source of TRS i pulping. These arelarge volume but lower concentrations (around 100 ppm) discharge In the steam and recovery section, the recovery boiler is the major source of TRS release, itis a high volume but moderate concentration (several hundreds pomw betore Control) source. In addition to the recovery boiler, the vent gases from the black liquor ‘evaporators and the «melt dissolving tank vent are other major sources of TRS emission While the vent gases from the black liquor evaporators is a low volume and high concentration {in excess of 100,000 ppm), the smelt dissolving tank is normally a source ‘of medium volume and low concentration TRS The effivent treaiment system can also be a significant source of TRS if aeration is, ‘inadequate or foul evaporator or digester condensates are sewered. TRS concentrations ‘rom this source are typicaly in the part per billon range, 2.1.2 Sulphur dioxide ($0,) ‘The major source of SO, emissions is the kraft chemical recovery furnace, because of the combustion ofthe sulphur-laden black liquor fuel. Under certain conditions, somewhat similar quantities of SO, can be released tothe atmosphere, particularly when residual fue! bil is added as an auniliary fuel, SO, ean aleo be released fcom the lime kiln and smelt dissolving tank. Power boilers burning high-Sulphur fuels (fuel oll, non-condensible gases (NCG), etc) can also emit significant quantities of SO, to the atmosphere 2.1.3 Chlorine (Cl,) and chlorine dioxide (ClO) , and CiO, emissions cesult from their use in the bleaching of pulp These enissions are considered mincr in nature compared to TRS emissions. Typical Cl, concentrations before contro! woulc be 150 - 200 ppmv carried in a gas flow of 900 mtonne clair dry unbleached pulp, CIO, emissions occur from the bleach plant CIO, washers as well as from the ClO,generating plant Bleach plant emissions of CIO, betore control are typically 100-150 ppm by volume carried in a gas flow of 800 rm*Ronne of air dry unbleached pulp. Normally CIO, emissions from the generator plant are very low except during upset conditions. 2.1.4 Oxides of nitrogen (NO,) INO, is formed during the fuel combustion pracess by the carton hetween oxygen and rivoges (ia the fuel or ia the combustion ai) at elevated temperatures. NO, can be emitted ‘n-varying quantities rom specife sources in the kat chemical recovery system. The major Constituent formed is nitic oxide (NO). a smal portion of which can be oxidized to form ritcagen dioxide (NO,), NO, and N,O,, Together, these are classified as total oxides of ‘iogen (NO). Niagen oxde emissions from kraf process sources, such as the recovery furnace and lime kiln are normaly lower than for most other fuel combustion processes Tiss primarily de to the large quantities of water present in black liquor and line, which act a3 a heatsink to suppress the flame temperature, However. large quantiles ol nitrogen ‘odes can be formed when auxiiay fuels such as natural gas or fuel ol are adéed to the recovery furnace 2.1.8 Organic non-sulphur compounds (Organic compounds other than those containing sulphur can also be emitted in varying quantities from several diferent katt pulp mill process sources These compouncs include terpenes, hydrocarbons, alcohols. phenols and other organic compounds liberated from wood. The major process sources of non-sulphur organic compound emissions to the atmosphere include digester blew and relief gases. multiple effect evaporator non ‘condensible gases, brown stock washer hood and seal tank vents, black liquor oxtdation tower and storage tank vents, direct contact evaporators exhaust gases, digaster and ‘evaporator condensate vents, vaste water treatment facilities and paper machine coating land drier vents. Major process variables that atfect emission of these compounds to the lmosphere include the wood species being pulped or the type of coating materizl applied the organic or condensate stream temperature, the volatity of the organic or condensate ‘steam and, the type ang entectiveness of any ar polluton contro device. 2.1.6, Carbon dioxide and carbon monoxide ‘The pulp and paper industry is responsible for far less than 10% of the total Canadian discharge of carbon dioxide (CO,). The CO, discharge from fossil fuel by the pulp and paper industry accounts for about 2% of the total discharge of CO, from fossil fuels in ‘Canada, About 60% of the CO, generation within the industry results from combustion or Fegeneration of pulping liquor. Another 20% is derived from incineration of wood waste Carbon monoxide (CO), is the result of incomplete combustion. In general, in well controlled combustion processes, if there is enough excess air, CO formation is significantly reduced2.2 PARTICULATE EMISSIONS The major sources of particulate emissions from the kraft process are the recovery ‘tumace, the smett dissolving tank and the lime kiln, High particulate emissions can also ‘originate from wood waste power boiles. 2.2.1 Recovery particulate ‘The recovery boiler isthe largest source of particulate emission. The major constituent of the recovery boiler particulate is saltcake (Na,S0,, Na,CO,), 2.2.2 Smelt dissolving tanks particulate ‘The particulate emissions from the smelt dissolving tanks consist af sodium earbonate (Na,CO) and sodium hydroxide (NaOH). Typical rates of release o particulate from the ‘smelt dissolving tanks range from 2.5 to 35 kg per tonne of air dy unbleached pulp These emissions are corrosive due to their strong alkalinity 2.2. Lime kiln particulates The paniculate emissions from the lime kiln consist of calcium carsonate (CaCO) and calcium oxide (CaO). Typical rates of pariculate release trom the lime kiln can exceed 100 kg per tonne of air dry pulp, These emissions are alkaline and corrosive under moist conditions, 2.2.4 Power boiler particulate ‘Wood waste power boiler emissions consist primarily of carbon and unburned wood Particles. The quantiy of particulate emissions from wood waste boilers is highly variable ‘depending on operating conditions. Wood waste boiler emissions are a problem primarily due to property soiling 3. ENVIRONMENTAL IMPACT OF KRAFT MILL EMISSIONS. ‘The overall impact of emissions upon environment is largely dependent on their Concentration at ground level, Possible impacts are strongly influence by such factors as the concentration of emissions, the quantiies emited, prevailing meteorological conditions and loce! topography, as well as the duration and frequency of exposure. Air quality standards are enforced by the provincial governments and consideranle differences exist in their legislation (See Table I). The ambient air quality objectives for Briish Columbia are summarized in Table Il 3.1 Hydrogen sulphide Hydrogen sulphide has a “rotten egg" adour. It is typically considered the most identiiatie emission from a kraft mil. Ambient air quality objectives are principally based ‘upon the nuisance aspect of odour, since odour perception is as low as 0.47 ppb for some individuals. The twreshold limit value (TLV) was set at 10 ppm by the American Conferenceof Governmental Industrial Hygienists after careful consideration of all available medical and toxicological information. This standard implies that repeated exposure to 10 ppm H,S causes no harmful health effects to people. In British Columbia, the Workers ‘Compensation Board (WCB) accepts 10 ppm H,S as a maximum allowable exposure over an eight hour period for a worker. At ambient concentrations near 100 ppb, some individuals ceport discomfort, insomnia, nausea and headaches. H,S can be toxic to certain types of vegetation but nat to others, 3.2 Methyl mercaptan “There is litle information available on the effects of methyl mercaptan upon receptors, ‘Methyl mercaptan is believed to act like H,S and to have a similar, but lesser, toxicity. No ‘effects, other than reactions to its nuisance odour, should be expected at concentrations found around a pulp mil, Methy! mercaptan has an odour similar to H,S, but itis more penetrating and abrasive to the senses. i smells ike “rotten cabbage’. thas a lower TLV in the workplace because it may mask the presence of H,S. The effects of likely ambient concentrations of methyl mercaplan on receptors is not ‘well known, and work done by different investigators is dificult 0 compare Perhaps 20% of all kraft ill TRS emissions are methy! mercaptan 3.3 Dimethyl sulphide Dimethyl sulphide is considered an objectionable emission ofthe kraft mill industry, but tis a government-approved flavouring agent in Canada and in Britain, There is no specific ambient air quality objective for dimethyl sulphide. It is included as TAS. The odour detection level is similar to that for methyl mercaptan and lower than that for H,S. Limited data suggests that dimethyl sulphide is up to 60 times less toxic than methyl mercaplan 3.4 Dimethyl disulphide Dimethy! disulphide is not specifically egulated and is included in TRS guidelines. The only available data comparing the toxicity of the TRS compounds suggests that dimethyl isuiphide could be two to five times less toxic than hydrogen sulphide 3.8 Chlorine and Chlorine dioxide ‘Although chlorine and chlorine dioxide are hazardous in high concentations. there is litle information to suggest that normal ambient concentrations cause environmental damage. These pungent gases would be detected by most people at lower concentrations than 0.5 ppm. There is no information to suggest that chorine dioxide is more toxic than chionne. The WCB maximum allowable concentration for eight hour exposure to chlorine 4s 1 ppm, while that for chlorine dioxide is 0.1 ppm. Short-term exposures of humans to these gases may cause irritation of the eyes and nose, however, the effect is temporary after the source of ititation has been eliminated.3.6 Sulphur dioxide Ambient air quality objectives are set to protect the most sensitive receptor which, for SO,. is vegetation. Sulphur dioxide is an iritant for man and animals at concentrations above 5 ppm. In the presence of particles, high humidity and other factors, he iriation level could be reduced to 0.5 ppm, but itis presently impossible to establish a no-ettect level. Athough SO, is a major concern for acid rain, SO, emissions from kraft mills are not considered to be significant contributors to this global problem. 37 Nitrous oxides NO, contribute to acid rain and reacts in the presence of sunlight to form low level ozone, of smog. Kraft mills NO, contribution to acid rain is relatively minor. 3.8 Carbon monoxide and carbon dioxide CO and CO, are two odourless gases. CO is toxic and CO, is not. The B C Worker's Compensation Board threshold limit values for eight hours exposure is SO and 5000 ppv for CO and CO, respectively. Although CO, is the principle component of the greenhouse ‘gases (earth warming), itis also needed for plantation growth 3.9 Particulates Kraft mill particulate emissions appear to have Iitle environmental impact wa the quantities discharged. Very small saltcake particulate has a diameter simular to the wavelength of visible light and causes a persistent plume. Interaction with SO, makes these paniculates more visible since they serve also as nuclei for moisture condensation and contribute to haze. Wood particulate emissions may create a “blue haze" in the atmosphere. This flyash could be a soiling problem. Salt in the particulate plume can contribute to the visibility of stack plumes.