TI-2 Chemical Committee Informative Report No. 10 C. J. Lewis Colorado School of Mines Research Foundation, Inc. and B. B.

Crocker Monsanto Co.

The Lime Industry's Problem Of Airborne Dust

Informative Report No. 10 dealing with the lime industry's problem of airborne dust is one of a series of survey reports prepared by APCA's TI-2 Chemical Committee on air pollution problems and control measures encountered in the chemical industry today.

The usual products of the lime industry are limestone, quicklime, and hydrated lime. Limestone is rock composed of at least 50% calcium carbonate and various impurities. A common impurity is magnesium carbonate; when present in less than 5%, the limestone is referred to as high-calcium. A limestone containing 30-45% magnesium carbonate is classified as dolomitic stone. Table I gives composition of typical limestones of both types. Quicklime (CaO or mixtures of CaO and MgO) is produced by heating sized limestone to decompose the carbonate releasing CO2 and leaving the oxide be-

Table I. Typical analyses of high calcium and dolomitic commercial limestones. _ Calcium Dolomitic Calcium carbonate (CaCO3) Magnesium carbonate (MgCO3) Iron oxide (Fe2O3) Aluminum oxide
(AI2O3) Silica (SiO2) plus acid insolubles Loss on ignition (CO2) 97.40 1.25 0.11 0.35 0.95 43.40 52.34 47.04 0.04 0.20 0.26 47.67

hind. Hydrated lime is produced by reacting the oxide with water to produce the corresponding hydroxide. Table II gives the equations for the major chemical reactions involved in the lime process. During the calcination of limestone, moisture, and volatile organic matter are first driven off. At higher temperatures, the partial pressure of CO2 increases and decomposition of the carbonate begins. Decomposition does not progress at a rapid rate, however, until a temperature range of 700 800 C is reached for dolomite and 830 930 C for high-calcium stone.1 The loss of carbon dioxide during calcination leaves the residue in a porous, highly reactive state. It is usually the desire of the manufacturer to remove the lime oxides from the kiln as close to the upper limit of the decomposition temperature as possible. Subsequently heating results in shrinkage and loss of chemical reactivity. Sufficiently high heating results in a material of low reactivity referred to as "dead burned" lime.
Occurrence, Location, and Uses

posits exist in every state in the U. S. but only a small portion is of sufficient purity for industrial use. The lower grades are generally suitable for agricultural purposes. Better than 90% of the limestone quarried is from openpit operations with the remainder from underground mines. Lime manufacturing plants vary in: (1) the relative emphasis given to potential products (Limestone, lime, and hydrated lime); (2) whether the product is for commercial sale or for captive use (i.e., an integral operation of sugar manufacture, steel production, soda ash manufacture, pulp and paper manufacture, etc.); and (3) type of kiln used (vertical, rotary, other). Figure 1 shows the distribution of commercial lime plants in the contiguous U. S. The split in production between limestone, lime, and hydrate will vary considerably from plant to plant. However, the distribution between all plants in the year 1964 was: Limestone Lime Refractory Lime (dead-burned) Hydrated Lime 510,025,000 tonsa 11,400,000 tons 2,150,000 tons 2,600,000 tons

Limestone is the usual raw material for manufacture of lime products although a small percentage is manufactured from oyster shells, particularly along the Gulf Coast. Limestone de-

"Includes limestone further processed to lime products.

Informative Report No. 10 of the TI-2 Chemical Committee was first submitted to APCA's Steering Committee and Technical Council on September 18, 1967. It was processed in accordance with the 14 step procedure outlined in the March 1963 Journal and was finally approved by APCA's Board of Directors on December \r 1968. In accordance with the objectives of the Association as they appear in Article XV, Section 4 of the By-Laws, each technical coordinating committee has the task of reviewing and amending its studies as often as necessary in the light of technological changes. In accordance with procedures adopted by the APCA Technical Council and the Board of Directors, it is now published as representing "the best thinking of the Association."
January 1969 Volume 19, No. 1

Table II. Theoretical equations illustrating reactions in lime manufacturing. 1. High calcium (a) CaCO3 + heat CaO + CO2 ' (limestone) (lime) (carbon dioxide) (b) 2CaO + 2H2O - 2Ca(OH)2 (lime) (water) (hydrated lime) (c) CaCO3-MgCO3 CaO-MgO + 2CO2 t heat (limestone) (dolomitic lime) (carbon dioxide) (d) CaO MgO + H2O -> Ca(OH)2-MgO (dolomitic lime) (water) (dolomitic hydrate, partially hydrated) (e) CaO-MgO + 2H2O -4Ca(OH)2-Mg(OH)2 (dolomitic lime) (water) (dolomitic hydrate, completely hydratad) 31 2. Dolomitic

Table III. Uses of quicklime and hydrate in 1964. Tons Agriculture Building Metallurgy Alkali Carbide Sugar Water purification Pulp and paper Glass Sewage treatment Soil stabilization Miscellaneous chemical uses Refractory Lime Total Figure 1. Distribution of commercial lime plants. 200,000 908,000 3,303,000 3,382,000 959,000 852,000 910,000 843,000 302,000 201,000 450.000 1,675,000 2,168,000 16,150,000 Percent 1 6 21 21 6 5 6 5 2 1 3 10 13 100

Only about \% of the limestone is sold in the form of dimension stone, the rest being sold crushed or broken. Over 60% of the crushed stone is used in construction for concrete aggregate, road and railroad ballast, and riprap. Around 8% is used in chemical and metallurgical industries as a flux in the manufacture of iron and steel, acid neutralization, alkali production, sugar manufacture, calcium carbide production, pulp and paper manufacture, and as a product filler. Eighteen per cent is used in cement manufacture, 5% in calcined lime products, and the remainder is used in agriculture for reducing soil acidity and providing neutrients and in animal feeds. Quicklime and hydrate are used interchangeably to some extent. Taken together their distribution by use in 1964 is shown in Table III. The agricultural use is primarily for soil liming. Building use is split roughly evenly between plaster and mortars. Refractory lime, which is all dead-burned dolomite, is used in manufacture of dolomite brick and in open hearth steel furnace bottom lining.
Manufacturing Operations: Mining

is as objectionable as the dust. Fortunately, most quarries are in rural or somewhat isolated areas. The loading and unloading of the blasted stone can also release dust into the atmosphere. While many plants currently make no effort to contain this dust, wetting of the broken stone with hoses or sprays can effectively decrease it. While it has not been investigated, the addition of wetting agents to the water should improve the penetration of water into the broken rock. Too much wetting of the rock may be objectionable in that it can interfere with subsequent grinding and sizing operations. However, wetting of the surface of the load in the truck or car will greatly reduce windage loss during transport. If transport of the stone is by truck, attention should be given to the creation of airborne dust from unimproved mine roads. This can be greatly minimized by frequent wetting of the roads during dry weather. The need for constant sprinkling of the roads can be greatly decreased if oiling or wetting with calcium chloride solution is used. Paving,

of course, is a desirable alternative. Underground mining of rock releases less dust to the atmosphere because most operations are confined. However, it is more expensive and wasteful of high grade rock because pillars must be left. Less than 8% of the limestone produced is mined underground.
Stone Preparation

The extent of preparation given to stone received from the quarrjr depends on the end use. For riprap, no preparation at all is required, but most applications require reducing the limestone to rigid size specifications. Concrete and road aggregates must be crushed, cleaned, and graded to size. Pulverized limestone must frequently be ground to a fineness of 65-100% passing 200 mesh. Lime manufacture requires stone of definite size ranges depending on the type of kiln used. Preparation of crushed stone requires a series of crushing, screening, and classification operations. Primary crushers will normally be of the jaw or gyratory type, although roll crushers and hammer

[FINES]

^PULVERIZING

COMMERCIAL PRODUCTS

Figure 2 presents a generalized flowsheet for a typical lime manufacturing operation. A variety of mining and quarrying methods are used with various types of equipment. In obtaining broken stone, the usual operations involved are: (1) drilling holes for explosives; (2) blasting the limestone loose; (3) loading it into trucks or cars; and (4) conveying it to the crusher. Dimension stone is quarried by sawing and cutting, and is not used for lime manufacture. Open pit quarrying of limestone produces dust which is released into the atmosphere during blasting. Quantities of such dust, which is released intermittently, have not been reported. There is little that can be done to confine this dust as long as blasting is the means of shattering the rock loose. Often the noise produced
32

LIMESTONE MINE OR QUARRY

CRUSHING AND SCREENING

STOCKPILES

COMMERCIAL PRODUCTS

LIME KILN FEED

COMMERCIAL PRODUCTS

LIME MANUFACTURING KILN

LIME CRUSHING AND SCREENING

LIME STORAGE BINS

GRINDING AND PULVERIZING

COMMERCIAL PRODUCTS

-HUMEHYDRATOR FEED

f
GRINDING AND/OR LIME HYDRATOR * > AIR CLASSIFICATION HYDRATE STORAGE BINS COMMERCIAL PRODUCTS BULK LOADING AND/OR BAG LOADING

Figure 2.

Flow sheet of a typical lime manufacturing operation. Journal of the Air Pollution Control Association

EXHAUST

PEHEATING ZONE

CALCINING ZONE

FINISHING ZONE BURNERS-

mills may be used if the stone is soft and friable. Frequently, the primary crusher will be located at the quarry or mine with a stockpile of crushed stone being maintained nearby to cover periods when the quarry is not in operation. Primary crushers will normally reduce stone to 1 - 3 inches in size. Secondary crushers are normally used to reduce stone to sizes below one inch. These are usually cone crushers or highspeed, flat-angle gyratory machines. Hammer mills may be used if the stone is not abrasive. For pulverizing, a hammer mill, rod, ball, or tube mill, or an edge-running roller mill may be used. For extreme fineness, closed circuit grinding in air-swept mills with air classification is required. Occasionally, stone may be dried in a rotary dryer to assure better grinding. Vibrating screens are normally used for classifying smaller sized stone exceeding 50 mesh. Where accurate sizing of larger stone is not required, bar grizzlies are normally employed. Air classification is the normal means for veryfineor pulverized sizes. Stone is normally transported between operations on open-belt conveyors, although bucket elevators, drags, screws, and pneumatic conveyors may be used occasionally. All of these operations give rise to production of limestone dust. Many plants in isolated areas carry out these operations without pollution control equipment and many more have only the crudest kind of collection system for the coarser size operations. The best control would dictate corrugated covers over the belt conveyors to reduce windage losses, careful hooding at transfer points connected to air exhausters, and hooding or evacuating of crushing machinery to eliminate dusting. Many plants currently collect the dust from exhaust systems with simple cyclones, or water spray chambers. With tighter control regulations, it is likely that many of these must be improved, making use of bag filters and more efficient wet scrubbers.
January 1969 Volume 19, No. 1

DQOOQD

COOLING ZONE

STORAGE ZONE

El
Figure 3. Vertical lime kiln.

Data on losses per ton of material handled has generally not been determined or reported. However, particulate losses from control equipment currently in use at a number of plants is shown below in terms of dust concentrations leaving control equipment:
Particulate Type of Control Loss (grains Equipment per cu. ft.) 2.0 Cyclone Water Spray Collector None Water Sprinkling Cyclone and Bag Filter 0.016 0.165 0.002 0.054

Operation Pulverized limestone dryer Primary crushing Screening Stockpile Secondary crushing

Lime Production

A number of types of kilns are available for carrying out the calcination reactions. They differ in their configuration, fuel economy, size stone required, inherent capacity, and efficient use of manpower. Slightly more than 50% of lime production is in rotary kilns and the trend is in this direction. Verticle Kilns. This is the oldest and most numerous type of continuous kiln in use and one of the most efficient in fuel utilization. The major drawback is that it is inherently restricted to low capacity per unit. For this reason there have been few recent installations. Almost all modern installations have utilized rotary kilns or one of the newer design calciners. A cut of a typical vertical or shaft kiln is shown in Figure 3. These kilns usually have a steel-encased refractory shell 10-24 ft in diameter and 35-75 ft in height. An inclined skip-hoist is

frequently used to convey the stone to the top of the kiln where it is charged in batches. The kiln is usually fired with burners in the side, utilizing gas or oil. Some older kilns contain a firebox on the side where coal is used. These kilns utilize heat very efficiently because the cold stone at the top cools the flue gases while the hot stone at the bottom is cooled by air used for combustion. The calcined lime is withdrawn at the bottom either in batches or continuously with suitable feeders or gates while the flue gas exhausts at the top. In some plants where coal is used as fuel, it is mixed with the limestone or charged in layers and burns within the kilns. This technique is used mainly in captive plants such as in the alkali and sugar industries where lime purity is unimportant and the CO2 produced is one of the desired products. Most vertical kilns require limestone in sizes of 6 - 8 inches to minimize pressure drop. Because of the large stone size, low capacity, and low gas velocity through the kiln, many of the older kilns were open on top with no provision to collect the gases and control atmospheric emissions. Captive kilns, where the CO2 produced is needed for processing operations in the alkali and sugar industry, are closed on top with a doublebell seal much like the charging mechanism of a blast furnace. Except for occasional leakage through the charging seal, these kilns emit no gases or dust to the atmosphere. They are conducted to processes not involving lime manufacture. Particulates in these gases enter the other process equipment.
33

There is no reason other than cost why non-captive vertical kilns cannot be sealed in similar fashion with the exhaust gases conducted to suitable dust control equipment before release to the atmosphere. Many older vertical kilns have capacities of 7-15 tons per day of lime produced. However, the trend has been to larger capacity gas-fired kilns producing 75-80 tons per day and many of the older kilns have been converted to kilns of this type. Rotary Kilns. This is the same type of kiln as is used in the production of Portland cement. Its general advantage is that it has the highest capacity of any type kiln available. Some rotary kilns have achieved production rates in excess of 500 tons of quicklime per day. This greatly reduces the manpower required per ton of product. Disadvantages are that capital investment is much greater for rotary kilns and fuel economy is poorer than for vertical kilns. Typical rotary lime kilns vary in size from 6 to 11^2 ft m diameter and from 60 to 400 ft in length, though 150 ft is a common length. Rotary kilns are most commonly fired with gas, oil, or pulverized coal. Modern kilns are generally highly instrumented for efficient control of temperatures and combustion conditions. The flow of stone and combustion products is countercurrent through the kiln. While the feed end of the kiln may cool the hot gases by preheating the stone, the kiln usually discharges the quicklime quite hot. For this reason, product coolers are usually provided to preheat the combustion air. Heat efficiency may also be improved sometimes through the use of chain sections and preheating tubes at the feed end. These devices will also tend to reduce the loss of particulates which would otherwise be carried out in the exhaust gases. Rotary kilns require a more carefully classified and smaller size limestone than vertical kilns. The feed generally ranges in size from M to J^ inches. In plants with more than one rotary kiln, frequently one kiln will operate on }i inch stone with the others on 1 to 2y2 inch size. This leads to greater uniformity in the product. New Type Kilns. Since World War II, several new types of kilns have been introduced. The Dorrco Fluosolisd kiln2-6'7 calcines fine particle size limestone in afluidizedbed. Limestone particle size must be 6 mesh or less. It has high capacity, excellent temperature control, and good fuel economy. The Ellerbeck kiln3 is a modified
34

rectangular shaft kiln which claims low capital investment in low-capacity sizes of 6 to 15 tons of lime per day. It produces a 3- 1J^" size pebble lime. Roberts4 reports a modified captive shaft kiln with internal combustion chambers having a capacity of 600 tons per day. Lime kilns recently installed using a combination of traveling grates and rotary kilns have been discussed by Kohanowski.8 The Calcimatic9-10 kiln is a new development in which after preheating of the charge in a vertical feed hopper with the exhaust gases, the stone is deposited in a thin layer on a traveling circular refractory hearth. The stationary stone on the revolving hearth travels under a series of combustion chambers and is finally scraped off to a product cooler just before the hearth returns to the charging point. Because the stone is stationary during calcining, there is little attrition and dust generation. The kiln can handle stone in sizes from }4 inch to 4 inches, can use either gaseous, liquid, or solid fuels, and is available in capacities from 100 to 500 tons of lime per day. Product Handling. After cooling, the quicklime from vertical kilns is usually inspected to remove "cores" and unburned stone. This is a hand operation performed by workmen as the quicklime passes by on a conveyor belt. Much of the quicklime is then sold and shipped in bulk hopper cars in this form. However, it may also be subjected to screening and milling operations to produce a sized pebble or ground quicklime. Airswept hammer mills are usually used for grinding. The comments under Stone Preparation concerning dust control also apply to these operations.
Hydrated Lime

in which a modified rod mill called a plasticitor does the final milling. Hydration of lime is also carried out in agitated equipment using great excesses of water so that a slurry or "milk of lime" solution is produced rather than a dry powder. This operation is usually referred to as slaking rather than hydrating. Slaking equipment will usually be located at the plant of the lime user but will seldom be found at the installation of the lime producer unless he has a captive use. In terms of air pollution, the slaker has a considerable advantage over the hydrator. Due to the large excess of water used, no steam is given off and no gases are discharged which can carry out entrained lime dust.
The Air Pollution Problem

Hydrated lime is produced by adding water to crushed or ground quicklime while mixing in order to produce intimate contact. An excess of water is added because much water is lost as steam in carrying off the heat of hydration. The dry hydrated lime produced is usually milled in an air-swept hammer or ring-roll mill. Uncalcined stone called "core" and silica are usually removed in the air separator of this mill. Standard hydrated lime usually has a fineness of 95% passing 200 mesh. Some production, designated superfine, is pulverized and/or air classified to 993^% through 325 mesh. A major portion of hydrated lime is packed in paper bags, but some is shipped in bulk. The literature5 describes one hydrate plant

The major air contaminant from lime operations is dust; limestone dust from mining, handling, crushing, and screening operations; quicklime dust from kiln discharge, handling, shipping, and milling operations; hydrate lime dust from hydrator operations, milling, and packing. These dusts are generally looked upon by the community as a nuisance rather than endangering health. Pulverized limestone is applied in copious quantities in many coal mines as an inert material to minimize coal dust explosions. Farm workers are often exposed to hydrated lime dust during soil application. The building trades are frequently exposed to both dust and wetted lime products without detrimental effect. Silicosis and respiratory ailments are not a problem among lime plant workers. On the other hand, lime (both quick and hydrate) are alkaline substances and, as such, can be irritating to eyes, respiratory membranes, and moist skin. For these reasons as well as the nuisance value, emission of these materials is objectionable even though they cannot be placed in a hazardous class. Most lime manufacturing plants started operations in a location well removed from residential areas and their property lines extended hundreds, even thousands of feet beyond the manufacturing plant to encompass limestone ore reserves. Farms in the vicinity welcomed, as many still do, the fall-out of "lime" dust as a soil sweetener or soil conditioner. However, the increasing perimeter of urban areas, the advent of new highways through or adjacent to lime manufacturing properties, air observation of effluent plumes and the increasing sensitivity of society to air pollution have combined to focus attention on lime plant

Journal of the Air Pollution Control Association

dust emission. Accumulation of lime dust around the plant results in an unsightly operation; it settles on foliage, home roofs and walks, clothes on the line, window sills and lawn furniture, to cause local indignations; and when it settles on polished cars or enters the air intakes of other manufacturing concerns, it may cause financial loss. These factors are requiring lime operators to pay more attention to their particulate losses. Like all other fuel users the lime manufacturer must also give consideration to control of contaminants which are common to all combustion operations. Specifically, he must be prepared to reduce pollution from SO2 and SO3 (either by changing fuels or recovery equipment) if he is using a sulfur-containing fuel such as coal or fuel oil. The time may come when he will have to consider the generation of oxides of nitrogen, and, of course, if burning coal, he must worry about fly ash collection and incomplete combustion resulting in soot and tars.
Pollution Control Objectivies

Location of units of the lime manufacturing industry range from areas which may be designated as: (a) isolated; (b) undeveloped; (c) partially developed; (d) mixed industrial residential; (e) mixed heavy industrial ^residential; to (f) built-up residential. Air pollution control measures taken by the industry range from no control whatsoever to the most modern of dust collecting and dust disposal systems. Over the years, the industry has had no reliable barometer, other than local opinion, for assessing the societal aspects of its dust emissions. For the most part, the industry has followed the "good neighbor" policy with reference to dust control procedures. These have laboriously evolved rather than erupted and there is no fixed pattern. This situation is changing, however, as federal and state involvement in pollution grows. An examination of current and proposed air pollution legislation suggests that lime plant effluent will probably have to comply with regulations on Particulate Emission, Visibility, Fuel Limitations (if a sulfur containing fuel is burned), and possibly Settleable Alkalies.
Particulate Emission

Many codes have a general limitation of 0.3-0.4 grain of dust per standard cubic foot of exhaust gas. In addition, many codes have a further limitation
January 1969 Volume 19, No. 1

applying to combustion operations which is primarily directed to control of coal fired boilers. Initially, most of these were based on the ASME (1949) recommendation of solids emission not exceeding 0.85 lb of solids per 1000 lb of stack gas. Most of these codes are now being changed to a sliding scale which starts at 0.60 lb of solids per 1000 lb of stack gas for small boilers and decreases gradually with heat input to a lower level of 0.20 lb of solids per 1000 lb of stack gas for large utility boilers. Under some codes, it is not clear as to whether a requirement on combustion operations (and intended primarily for boilers) would also apply to a lime kiln operation where the combustion is incidental as a means of supplying heat for the process. Some of these ordinances require adjustment of the effluent quantity to 50% excess air or to 12% CO2 by volume in the effluent. Such an approach can also lead to difficulties in a lime kiln operation where the chemical reactions release CO2 into the flue gas. For instance, a 200 TPD lime kiln will also produce about 152 TPD of CO2 from the limestone calcined. For a pulverized coal fired kiln using a 1/4.0 fuellime ratio, the CO2 released from the limestone amounts to 22% of the total flue gases. It would appear that in adjusting the flue gas to some standard CO2 quantity that this should be done on a basis which adjusts the combustion products separately from the reaction products. However, not all legislation permits this. There is an increasing tendency in particulate emission legislation to relate quantities of dust emitted to process weight on a sliding scale basis which requires more rigorous control from large operations than from small ones. Process weight is usually defined as the hourly input weight of all raw materials including solid fuels, but excluding liquid and gaseous fuels and combustion air. A typical process weight table will permit release of 2.58 lb per hour of dust for a 1000 lb per hour process weight tapering off to 69.0 lb per hour for a one million pound per hour process weight. Under such a regulation, a 200 TPD lime kiln fired with bituminous coal having a 1/4.0 fuel-lime ratio would have a total process weight of 36,375 lb per hour (29,100 lb per hour of limestone and 7275 lb per hour of coal) and would be allowed to discharge 28.6 lb per hour of particulates. Such a process weight requirement would require the dust control equipment to have an overall efficiency of about 98.1%.

Visibility

Many codes impose an opacity requirement on the effluent plumes from operations which emit a non-black smoke. The majority of present codes permit a plume to be up to 40% opaque (equivalent to a Ringelman No. 2 for black smoke). However, there is a current tendency to tighten these requirements in proposed legislation to 20% opacity (equivalent to a Ringelman No. 1 for black smoke). Whether the visibility requirement is more restrictive than a process weight requirement is dependent on many things such as size of dust particles, total rate of emission of effluent, and stack diameter since opacity is a function of the distance one is trying to see through a plume. Present codes do not allow for differences in stack diameters. Another troublesome area under visibility requirements is the emission of high dewpoint gases containing dust such as the effluent from the lime hydrating operation. Steam evolved during the chemical reaction usually condenses in the atmosphere and makes the plume essentially 100% opaque. Some codes exempt an operation from the visibility requirement when the only reason for the operations failure to comply is due to the opacity produced by the condensing water vapor. Other jurisdictions prefer to observe the remainder of the plume in the atmosphere beyond the point at which all water vapor has dispersed. Even this presents difficulties of interpretation in that the water vapor tends to condense on the dust particles causing them to grow in size and be visible for longer distances. In any event, codes need to be carefully worded in regard to high dewpoint plumes to make their legal application clear in such cases. In the event the combination of condensing water vapor and lime dust is considered objectionable, two possible solutions exist. One is to lower the dewpoint of the effluent by dilution with atmospheric air. This is often prevented by the "Circumvention" clause of many codes. The other is to provide superheat in the effluent such that atmospheric diffusion occurs before condensation can occur. This will greatly improve the plume appearance without in the least reducing the contaminants released to the atmosphere. This is perhaps unfortunate as it wastes fuel and natural resources and adds to thermal and CO2 pollution of the atmosphere with only a compensating psychological benefit.
35

Sulfur Compounds

Table IV. Various fuel-line ratios from a pulverized bituminous coal-fired rotary kiln. Total Pounds of Gases Per Ton of Lime 17,095 12,390 8,744 6,920 5,826 5,096

The lime manufacturer will be concerned with these regulations only if he is using a sulfur-containing fuel such as coal or oil. Many new codes are presently placing limitations on the sulfur content of the fuel which can be burned or the ground level concentration of sulfur oxides.
Settleable Alkalies

Fuel-Lime Ratio 1/1.4 1/2.0 1/3.0 1/4.0 1/5.0 1/6.0

(by wt.) 33.0 35.3 38.9 42.2 45.1 47.7

%co2 in Gases

(by vol.) 23.9 25.8 28.9 31.8 34.3 36.8

Total Gas Volume (cuft@60F, 1 atm. per Ton of Lime) 203,500 146,200 101,500 79,200 66,100 57,000

A new unpublished and untried test which has been suggested in at least one legislative proposal would test quantity of dust fall on an indicator material that would be affected by the pH of the dust. The test would normally be applied upwind and downwind of the plant premises. A certain greater number of indicator spots would be allowed in the downstream sample. Very little experience has been obtained with such a test, but it might pose rigorous requirements on a lime plant should such test methods become more widespread.
Control of Specific Contaminants Dust from Limestone Processing

Dust, produced from quarrying, transportation, crushing and classification systems, is a heavy dust released at near ambient temperature. It has the same chemical analysis as the limestone being processed. The dust usually contains some moisture and the majority is of fairly coarse particle size which will generally settle within a thousand foot radius. Control measures consist of wetting and sprinkling to minimize dusting and proper hooding and evacuation to collect dust from crushing and screening equipment and transfer points. Cyclones or water spray chambers are the present chief means of collection of this dust. The majority of the dust which is larger than 20 microns is efficiently collected, but the finer particles released can travel several miles. For their control, it will be necessary to use bag filters or high efficiency water scrubbers. Control equipment is discussed under Rotary Kilns.
Dust from Lime Burning

Vertical Kilns. Many vertical kilns are of ancient vintage and were originally built without control equipment. They do not produce as much dust without control equipment as does a rotary kiln because of the larger size of the limestone charged, the "lazy" gas velocities, and the smaller amount of attrition which occurs as the charge passes through. Nevertheless shaft kilns are apt to be considered dusty by modern air pollution standards. Typical dust loading of untreated exhaust gas is in the range of 0.3 -1.0 grains per cu ft. For example, a 25 ton per day vertical natural gas fired kiln having a fuel economy of 6 million Btu ton of quick36

lime produced and an exhaust dust loading of 0.6 grain per cubic foot would release 7.7 lb per hour of dust to the atmosphere if using 10% excess air. Coal-fired vertical kilns have also been characterized by their emission of black smoke which may travel a mile or two. Captive vertical kilns used by the alkali and sugar industries are sealed because of the need for CO2 from the flue gas in other operations and hence emit no pollution as long as the seals are in good working condition. It would be possible to so equip commercial vertical kilns and use the control devices on the effluent gas which are used on rotary kilns. However, most of the vertical kilns are of small capacity and are becoming obsolete. The addition of control equipment in many cases could not be economically justified. Pressure to reduce their particulate discharge will in most cases hasten the day of their complete replacement with larger, more efficient kilns designed with adequate control equipment. Rotary Kilns. These kilns, when not properly equipped, constitute the largest single source of airborne particulate matter in the lime industry. Abrasion of rolling limestone charge in the kiln produces dust. The stone becomes more friable as it approaches the decomposition temperature and dusting increases. Finally, the resulting lime in the "hot zone" tends to be chalky and much less hard than the stone from which it is produced. Simultaneous with dusting from attrition, the high velocity gases from direct fire fuel combustion blow the dust from the kiln. This is a vexing dust to control and collect. It is hot, dry, difficult to wet, and prone to be electrostatically charged. It is of mixed composition varying all the way from raw limestone tofinalcompletely calcined product. It will also be mixed with fly ash, tars, and unburned carbon if pulverized coal is used as the fuel. The dust blown from a rotary kiln will range from 5 to 15% of the weight of the lime produced. Temperature of the exhaust gases leaving the kiln will range from 600 - 1800F. Typical exhaust temperatures for a 6 ft dia. kiln are 1350F "80" ft of length. This temperature will drop to 600 F if the kiln length is increased to 300 ft.

Gibbs11 indicates the following pounds of gases per ton of lime at various fuellime ratios from a pulverized bituminous coal-fired rotary kiln (Table IV). Data is based on a coal with a heating value of 13,500 BTU per lb. A typical 8 ft diameter by 220 ft long coal fired rotary kiln producing 200 tons per day of lime with a 1/4.0 fuel-lime ratio would exhaust about 1,384,000 lb per day of gases at 910F. Assuming a dust loss of 5% of the weight of the limestone charged (9% of the lime produced), a total dust quantity blown out is 36,000 lb per day without allowance for fly ash from the coal. This corresponds to a dust loading of about 0.026 lb of dust per lb of exhaust gas or about 15.9 grains per cu ft at 60F. Dust blown from a kiln also varies greatly with gas velocity. The literature16 reports doubling of the dust blown out when a kiln production rate was increased from 100 to 135% of design capacity while dropping production rate to 75% of capacity only dropped dust loading by 8%. The gases leaving the kiln are usually first passed through a dust settling chamber to break the gas velocity and settle out the coarse particles. On occasion, dry cyclones may also be used for this primary collection. From 65 to 85% of the particulate matter may be collected here. The primary dust is taken to a waste dump, used as land fill or for agricultural land treatment. Wetting before handling is advisable to reduce losses in dumping. An alternative is mixing with water and pumping as a slurry to a waste dump. Handling of the hot dust can create mechanical problems for discharge gates and conveyors. Bauer19 and Wolfe20 discuss design requirements for dust handling equipment. The major dust control problem is the dust passing the primary collector which is still hot (700-900F). A number of older plants in sparsely populated areas discharge the dust to the atmosphere through a stack where the 10-20 mesh particles fall to the ground in the immediate vicinity of the operation and smaller micron size particles are airborne for many miles. Obviously, such an operation can no longer be permitted in most locations and secondary control

Journal of the Air Pollution Control Association

equipment is mandatory. Table V gives the chemical and screen analysis of stack dust from a typical plant without secondary collection. If pulverized coal is used as a fuel, these dusts would also contain varying amounts of fly ash. A typical chemical analysis of fly ash products is shown in Table VI. Over the years, the lime industry has installed and studied almost every conceivable type of secondary collector.

Table V. Stack dust from two rotary natural gas fired lime kilns with only primary collection.
Chemical Analysis High Calcium Dolomitic Operation Operation 0.66% 0.97 23.06 66.32 1.40 1.22 6.37 Screen Analysis Tyler Mesh Size + 65 - 6 5 +100 100 + 1 5 0 150 + 200 200 + 270 270 + 325 - 3 2 5 + 400 400a
a

Many plants in areas with some local control of air pollution have installed high efficiency cyclonic secondary collectors. However, to meet modern requirements, plants are increasingly turning to wet scrubbers and glass bag collectors. Electrostatic precipitators have also been investigated and found satisfactory. However, economics in the lime industry are such that costly precipitators are apt to be avoided as long as scrubbers and bag collectors will give acceptable performance. Table VII lists data on a number of installations with secondary collectors. 1. Cyclone Collectors. High efficiency cyclones are more suitable as primary collectors and precleaners for removal of the plus 10 micron size dust. One installation reports handling 80,000 actual cfm of kiln gas at 450-500F and 30-35% moisture content in 72 nine-inch size cast iron cyclones with a pressure drop of 2H inches of water and 70% collection efficiency as a primary collector. Collins15 also reports 70-80% collection efficiency with small tube cyclones. 2. Bag Filters. A number of installations are reported making use of glass fiber bag collectors handling gas flows as high as 150,000 actual cfm at temperatures in the range of 350 - 550F, with average particle sizes of 25 microns after precleaning with dust settlers. For the larger gas volumes, the bag house is compartmented so that only one section at a time is cleaned. A twelve compartment bag house for a 500 TPD kiln is reported.11 The cleaning cycle (shaking is not employed with glass bags) depends on dust loading but is usually a 10-15 min cycle. Design air to cloth ratio with one compartment out for cleaning is in the range of 1.95:1 to 2.2:1. (Air to cloth ratio is defined as cubic feet of air per minute per square foot of filter cloth surface.) Since kiln gases are frequently discharged hotter than can

Component Acid insoluble Heavy metal oxides

(R2O3) CaCO3 CaO MgO CaSO4 Ca(OH) 2

0. 4 5 % 0..35 64,.30 7..23 28,.20 0 .27

be handled directly by the bags, it is usual practice to cool the gases by water spray, air dilution, or a combination. Insulation of the bag house is not usually required unless the moisture content of the gases is quite high, as might be the case with wet feed. Collection efficiency is almost 100% between bag cleanings as a thin layer of dust on the bag forms additional filtering media. Particles 5 microns and less in size are apt to be lost through the bag immediately after cleaning. Capital cost is reported to be $1.80 per cfm handled with operating and maintenance costs running $0.20 per cfm annually. Bag life up to two years is reported.16 General experience dictates that when bags start to fail, it is best to replace all bags in the unit. Otherwise, one will encounter a period where bags are failing weekly with resultant pollution and loss of production due to frequent shutdown for maintenance. 3. Electrostatic Precipitators. While the use of electrostatic precipitators tends toward the costly side for the lime industry, one installation has been reported using a single stage precipitator as a secondary collector at a capital cost of $1.25 per cfm. It handles 160,000 cfm at 450- 500F inlet conditions in which 90 - 95% of the inlet dust is minus 10 microns. It is designed with a gas velocity of 3.3 ft per second and a residence time of 5.2 sec and has an on-stream efficiency of 95%. 4. Water Scrubbers. Many types of water scrubbers are in use. Two installations have been reported17 in satisfactory operation utilizing a cyclonic multi-vane dynamic scrubber in which the gases are passed through a wet agglomerating fan between stages after initial removal of the coarser particles. One of the advantages of a wet scrubber is

l/Vt. % 0 .5 1,.5 3 .6 10,.0 9 .7 8 .4 7 .5 58,.8

Average particle diameter for the -400 mesh fraction is 5 -6 microns determined by Fisher Sub-Sizer.

Table V I . Typical limits of ash analysis of U.S. bituminous coals. Component SiO 2 AI2O3 Fe2O3 CaO MgO TiO 2 Alkalies Na2O & K2O SO., Wt. % 20-60 10-35 5-35 1-20 0.3-4 0.5-2.5 0.1-4 1-12

Table VII. Secondary collection of rotary kiln lime dust. Installation No. Primary collection Type of secondary collector
1

Dust chambers Dust chambers 9 in. Tube cyclonesa Dust chambers Dust chambers Glass bag collec- 4-stage cyclonic4-stage cyclonicSingle stage elec- Venturi scrubber tors dynamic scrubber dynamic scrubber trostatic precipiand cyclonic tator scrubber
9.5 4.3 4-7

Dust chambers Spray and impingement plate scrubber

16

Inlet loading gr/scfm 10.0 2.8-2.9 Outlet loading gr/scfm 0.001 0.071-0.080 Collection efficiency 99.99% 97.5% Pressure drop in secondary collectorinches of 4-5 8 water Primary collector consists of 9 in. tube cyclones. Inlet January 1969 Volume 19, No. 1

0.02 99.7%

0.22
95%

0.12 97-96.3%

0.3-0.4 97.5%

1-2 15 8 5-6 loading to cyclones, 14.5 gr./cf; outlet loading, 4.3 gr./cf; efficiency, 70%.

37

that it can include a pre-humidification section and eliminate the need for pre-cooling the gases. A typical installation for a 180-200 TPD kiln with 40-50,000 actual cfm @900 - 1400F and a 5-10 grain per cf dust loading, would require a 9 - 10 ft diameter scrubber 32 ft tall. Scrubbing water requirement is 4 gallons per 1000 cf of gas processed. Pressure drop is 8 inches of water which would be supplied by the integral wet fan. Since the fan also serves as kiln exhaust fan, excess power is required. For the 200 TPD kiln installation, fan bhp would be 150. Collection efficiency is stated to be 99.7%. Scrubber cost is reported to be $0.50 per cfm of cooled saturated exhaust gas for 304 stainless steel construction and $0.25 per cfm for carbon steel. Stuart and Bailey12 report 96-97% efficiency on dust removal from a 335 TPD kiln using a combination Venturi scrubber and cyclonic separator. A pressure drop of 7-11 inches of water was used. Inlet gas volume was 6062,000 cfm at 350F. Water supplied to the Venturi throat was 1500 gpm at 50 psig pressure. Cleaned exhaust gases were discharged at 160-165F nearly saturated with water vapor. Similar results are reported by Walker and Hall21 using flooded disc scrubbers. Gas volumes per installation have varied from 40,000 acfm at 400F to 100,000 acfm at 600F. Mockridge13 reports 97% efficiency on lime kiln dust contained in 26,000 standard cfm with 43^-53^ inches of water pressure drop using a combination spray and impingement plate scrubber. Such a scrubber handling gas from a 250 TPD kiln was 10 feet in diameter by 22 feet tall. The cleaned gases were discharged at 15O.F essentially saturated with water vapor. Porter18 reports 96-99% collection with a scrubber in which the gases are impacted against a water surface. While wet scrubbing of the gas may frequently be cheaper, problems can be associated with wet scrubbing which are
38

not present with dry collection. Among them are discharge of a hot, humid gas stream, plugging at dry-wetted interfaces, scale buildup, and corrosion problems which may not exist in the absence of water. The hot, humid effluent will condense in the atmosphere producing an opaque plume which may give the misleading impression that the operation is still a heavy dust emitter. Methods14 for preventing atmospheric condensation are available but costly. Care must be taken in the method of introduction of the hot dusty gases into the scrubber so as to assure quick wetting and quenching without entrainment of liquid into the inlet. Areas which may be alternately wet and dry will accumulate dust with resultant caking and buildup, which may ruin efficiency or completely seal off gas flow. Instances17 are known where lime kilns had to be shut down every 5 days to clean out cakes and obstructions in home-made wet scrubbers. The presence of sulfur in the fuel or sulfates in the stone can result in sulfur oxides in the kiln exhaust. These can react with lime dust to produce slightly soluble calcium sulfate. Since calcium sulfate has an inverse solubility at higher temperatures, too little make up scrubber water or too high a water temperature can result in plating out scale deposits on metal parts of the scrubber. The presence of the sulfur oxides may also dictate the use of corrosion-resisting alloys for wetted parts. Since placing the kiln exhaust fan before the scrubber will subject it to the hot abrasive kiln gases, it is normally desirable to locate it after the dust collector. In the case of a wet scrubber, it may be necessary to make the exhaust fan of alloy construction as well. Some producers16 report operating costs for a wet scrubber three times as great as for a bag filter even though initial cost is considerably less. It should also be considered that slurry discharged from wet scrubbers is a potential water pollutant if not properly confined or consumed. Other Kilns. Data on dust emission from new kiln processes is largely lacking. Grate type kilns are stated to produce less dust than rotary kilns.

Fluosolid kilns emit copious quantities of dust in the exhaust gases and require very efficient dust control equipment. Plants using the Calcimatic Process appear to be remarkably free of dust since the stone is stationary during calcination on a revolving hearth. The major sources of dust are the exhaust from the stone preheater, the lime cooler, and the discharge lime conveyor. Bag filters have been found to be most practical for dust collection at the latter two sources. High efficiency cyclones have been used on the preheater exhaust, but glass bag filters would be the desirable collector for high collection efficiency. Data on a typical installation using a glass-filter bag house is: Exhaust gases, actual volume and temperature 20,000 cfm @600F Dust loading, 2.5 grains per cu ft Dust screen size 0-2.5 microns, 1.2% 2.5-5 microns, 2.1 5-10 microns, 3.4 10-20 micrens, 5.6 20 - 44 microns, 5.1 +44 microns, 82.6 Design gas to cloth ratio, 2.50:1 Typical bag life, 6 months Collector installed, cost, $3.60 per actual cfm Collection efficiency, 99.2%
Dust from Lime Hydrating

Lime and water react exothermally, often violently, in the hydrator to produce a crude semi-dry finely divided hydrated lime powder. Steam and moisture laden air sweep fine dust from the hydrating operation into the exhaust stack. High calcium hydrators operate at ambient pressure with "lazy" exhaust gas velocity. Pressure dolomitic hydrators discharge steam, air, and product through small orifices to maintain the pressure created by the reaction, and thus impart a high velocity to the exit gases. The dust from the operation will have the same analysis as the hydrate being produced. If not collected, it will carry a mile or two when airborne. On settling, it will slowly react with the carbon dioxide of the air to revert to calcium and magnesium

Journal of the Air Pollution Control Association

Summary Table VIII summarizes the dust loading in various effluents from lime plants resulting from an industry survey. carbonates. Because of the large amount of steam generated during the reaction, the discharge from a hydrator will be opaque. This makes it difficult, visually, to determine the amount of solids entrained in the steam. The loss of hydrated lime dust represents the loss of valuable product since this dust is of high purity. It is easily wetted and can be scrubbed from the stack gases with a water scrubber. The recovered water slurry can be fed back to the hydrator as make-up water so that handling of the recovered product does not represent a problem. Practically all lime hydrating plants are equipped with recovery equipment of one type or another. A common method is to install water spray nozzles in the exhaust stack and to add all or a part of the water to the hydrator in this manner. The scrubbing effect of the sprays plus steam condensation on the dust particles induced by the cold spray water, causes the particles to grow in size, be impacted by the spray, and settle back into the hydrator. Tests on plants utilizing such simple control procedures give dust loadings in the effluent in the range of 0.01 to 0.94 grains per cu ft. The large variation is probably due to differences in spray pressure, stack velocity, liquid to gas rate, and number of spray stages. Other plants have used recirculating Venturi-ejector scrubbers or other commercial wet scrubbers. Tests on commercial wet scrubber installations (not designated by type) have given effluent loadings of 0.01 - 0.03 grains per cu ft. Unfortunately, the discharge from efficient wet scrubbers will usually still be opaque with condensing water vapor. The treatment of hydrate following hydration is usually milling and air classification. Conventional air-swept equipment is used for this purpose and if kept under the proper suction with a bag filter and exhaust fan, will give no problem. Conventional bag filters with cotton bags will give 99+% recovery. Since the majority of these would be shaken only every few hours, the bleed through immediately following shaking is not serious.
January 1969 Volume 19, No. 1
Table VIII. Reported dust emission values from lime plant operations. Particulate Emission Grains Collection Efficiency Per Cu. Ft. 0.016 0.054 0.002 2.04 0.165 0.009 0.3-1.0 0.001 0.07-0.08 0.02 4.3 0.22 0.12-0.25 0.3-0.4 0.02 0.2-0.8 0.01 0.01-0.94 0.072 0.01 0.02 0.036 No visible dust 0.01 Poor Good 60 - 70%

Operation Limestone primary crushing Limestone secondary crushing Crushed stone stockpile Pulverized limestone dryer Limestone screening Bulk loading Stone unloading Vertical lime kiln Rotary kiln Rotary kiln Rotary kiln Rotary kiln Rotary kiln Rotary kiln Rotary kiln Calcimatic kiln Lime conveyingtransfer points Lime distribution systemairveyor Hydrating Hydrating Hydrating Hydrating Hydrating Hydrate milling Hydrate loader and packer

Control Method Water sprays Cyclone and bag filters Water sprays Cyclone collector None None Water sprays None Glass bag filter 4 Stage cyclonic scrubber 4 Stage cyclonic scrubber High efficiency cyclones Single stage precipitator Venturi scrubber Impingement scrubber Glass bag filter Cyclone collector Cloth bag filter Water sprays in stack Wet scrubber Wet scrubber Wet scrubber Wet scrubber Bag filter Bag filter

99.99 97.5 99.7 70.0 95.0 96-97 97.5 99.2

99+

99+ 99+

Bibliography

1. Murray, J. A., Fischer, H. C , and Shade, 11. W., "Thermal analysis of limestone," paper presented to the Nat'l Lime Assoc, Washington, D. C. (Spring 1950). 2. White, F. S., U. S. Pat. 2,465,410 (Mar. 29, 1949) (to Dorr Co.). 3. Ellerbeck, T. 11., U. S. Pat. 2,451,024 (Oct. 12, 1948). 4. Roberts, J. E., "Lime kiln design 1 UCM's vertical lime kiln," Chem. Eng. Prog., 59, 88-91 (Oct. 1963). 5. Anon., "Rockwell lime company operating non-pressure hydrator," Pit and Quarry (May 1956). 6. Havighorst, C. R., "Improved fluid bed calcination hikes lime production," Chem. Eng. 71, 104-6 (Oct. 26. 1964). 7. Shafer, M., and Brandt, M. W., "Lime kiln design 2hot cyclone development improves lime yield," Chem. Eng. Prog., 59, 95-99 (Dec. 1963). 8. Kohanowski, F. I., "Lime kiln design 3the grate kiln system," Chem. Eng. Prog., 60, 80-84 (Jan. 1964). 9. Law, C. and Hauser, P., "Lime industry gets boost from new kiln design," Chem. Eng., 71, 88-9 (June 8, 1964). 10. Anon., "Automatic kiln features moving hearth; Calcimatic," Can. Chem. Process, 49, 46 (Feb. 1965). 11. Anon., "River Rouge plant supplies Detroit steelmakers," Rock Products (July 1966). 12. Stuart, H. H., and Bailey, R. E., "Performance study of a lime kiln and

13. 14.

15.

16.

17. 18.

19.

20. 21.

scrubber installation," Tappi 48, 104A-108A (May 1965). Mockridge, P. C., "The use of Peabody scrubbers on lime kiln stack gases," Tappi, 255-256 (Apr. 1955). Crocker, B. B., "Water vapor in effluent gases: What to do about opacity problems," Chem. Eng., 75, 109-116 (July 15, 1968). Collins, T. T., Jr., "Pilot plant study of a multiclone unit operating on stack gases from a lime kiln," Paper Trade J., 126, 63-4 (Mar. 18, 1948). Wheeler, D. IL, Carlisle, J. L., Brousseau, G., Lacy, G. R., and Bergstrom, J., "Panel probes dust collection problems," Rock Products, 76-80 (Jan. 1965). Carlisle, J. C , "Texas lime tackles dust," Chem. Processing, 27, 46-47 (Sept., 1964). Porter, C. C., et al, "Elimination of lime stack losses with the type N rotoclone," Paper Trade J., 124*, 33-6 (Feb. 6, 1947). Bauer, W. G., "Factors of dust suppression in small to medium size rotary kiln systems," Pit and Quarry, 134-139 (May 1958). Wolfe, J. M., "Kiln dustproperties and handling," Pit and Quarry, 136145 (Mar. 1964). Walker, A. B., and Hall, R. M., "Operating experience with a flooded disc scrubbera new variable throat orifice contactor," APCA Paper No. 67-147, presented at the APCA 60th Annual Mtg, Cleveland, Ohio, June 11-16, 1967.
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