NZ216270A - Melting fusible material using ash-containing fuel as heat source - Google Patents

Abstract

Batch material for glass or ceramic is mixed with solid or liq. fuel which is combusted in pre-heating zone; ash and unmelted batch are passed to 2nd stage to melt batch, melting is then completed under oxidising conditions. Powdered material is heated so that source of O2 is supplied to combustion zone; gas and solid flows are co-current. Constituents not melting below 900 deg.C are mixed with fuel which is combusted to give 900 deg.C; mixt. of batch and ash is passed to 2nd zone and mixed with lower melting components and melting then completed. Batch for 1st zone includes alkaline earth carbonates which become calcined.

Description

216270 Priority Date(s): r.^r.^5 .^;.<o^5 Complete Specification Filed:^.^*.

CIas5< • • C6^S>/0.Q,|i*.vlfa Publica'io'1 Dale: ....?. ft !?®P..... P.O. Journal, No: . . ,'.%QG fawn"' NEW ZEALAND PATENTS ACT. 1953 No.: Date: COMPLETE SPECIFICATION "MELTING RAW MATERIALS FOR GLASS OR THE LIKE WITH FUELS CONTAINING ASH" fltfWe, PPG INDUSTRIES, INC, a corporation organized under the laws of the Commonwealth of Pennsylvania, United States of America, of One PPG Place, Pittsburgh, Pennsylvania 15272, United States of America, hereby declare the invention for which 4*/ we pray that a patent may be granted to)«£6ex/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by page -la-) 2 1 62 v MELTING RAW MATERIALS FOR GLASS OR THE LIKE WITH FUELS CONTAINING ASH Background of the Invention This invention relates to the use of solid carbonaceous fuels such as coal as a fuel source in a process for making glass or similar fusion processes and to the use of mixtures of solid or liquid fuels with the rav materials.

It is well known that in regions where coal is available It Is usually the cheapest source of energy relative to other traditional energy sources such as natural gas, fuel oil, a'nd electricity.

Therefore, it has been suggested that coal be used as a fuel source for melting glass and the like. Examples of such proposals may be seen in U.S. Patent Nos. 3,969,068 and 4,006,003. However, the use of coal to fuel direct fired process furnaces has been found to have certain drawbacks that have discouraged Its widespread use. A major drawback is the ash content of coal. When coal is combusted with an overhead burner In an open hearth type furnace conventionally employed to melt glass, substantial amounts of ash are entrained in the exhaust gas stream which can cause the regenerators to become plugged and which necessitates removal of the ash from the exhaust gas before it can be discharged to the atmosphere. Some of the ash becomes deposited on the walls of the melting chamber where it melts to a liquid slag that runs down the walls of the vessel into the melt. The runnage of molten slag has a deleterious affect on the refractories of the furnace, and the molten slag entering the melt introduces unwanted compositional variations and inhomogeneities into the product material. The slag often has a high 216270 % iron content relative to glass, and runnage of Che slag into Che melt can cause undesirable screaks of coloraClon. These problems have discouraged the use of coal as a direct fuel for melting products for which uniformity of composition is an important consideration. This is particularly the case with flat glass, where compositional variations F \ cause optical distortion in the product glass.

A drawback to the use of coal or other carbonaceous fuel in admixture with Che raw materials, particularly when melting clear glass, is chac carbon in amouncs sufficient to provide significant energy to Che melting process also has a reducing effect on the melt, and Iron and sulfur present in a reduced glass cause brown coloration. Moreover, coal itself contributes iron and sulfur to the melt. Small amounts of powdered coal (typically less than 0.1Z by weight) have been included in clear glass batch to aid the melting process, but such amouncs are noc significant energy sources, and larger amounts were considered detrimental. Even when brown glass is being produced, the amount of carbon employed would not be considered a significant fuel contribution.

U.S. Patent No. 3,294,505 discloses melting glass in a bed of batch briquettes and coke. The process is restricted to a relatively } narrow group of low viscosity glass compositions for low quality applications. Additionally, it would be desirable Co avoid the cost of agglomerating the batch. , > In US patent specification no. 4551161, i / there is disclosed a technique of wetting glass batch with fuel oil. Only a minor portion of the energy requirement of the melting process is supplied by the fuel oil.

Another problem with using coal and some other carbonaceous fuels is that such fuels contain relatively volatile hydrocarbon -2- ■ . V i V '■£ ' ~ - .n; 1 o JUL 1987! 2 16270 fractions chac are driven off and escape with che exhaust gas if heaced before ignition. This is a problem particularly if it is desired to preheat raw materials in admixture with carbonaceous fuel. Also, feeding carbonaceous fuels In a non-atomized form to a combustion zone generally produces smoke-laden exhaust that is environmentally undesirable. After-burning or otherwise treating the exhaust gas or carbonizing the fuel in a preliminary operation are costly options that are preferably avoided.

Summary of the Invention In one aspect of the present invention fuel having an ash content (e.g., coal) is employed as a substantial energy source for a melting process while avoiding the problems usually associated with the ash. The ash-producing fuel is combusted in a discrete batch preheating stage of the melting process where the ash becomes incorporated into the batch material. Preferably the batch material and the fuel are fed to the preheating stage in admixture wich each ocher Co establish disCribuClon of the ash throughout Che batch and to provide intimate contact between the batch and Che fuel during combuscion. Combustion is susCained by feeding an oxidant (preferably substantially pure oxygen) to a zone of combuscion in Che preheating scage. Agitation of Che macerial in Che preheating stage may be provided to enhance contact between the batch and the combusting fuel and to assist in mixing the ash into Che batch. The heated batch and ash mixture, preferably scill in a pulverulent state, is passed to a subsequent stage where the mixture is liquefied.

A significant portion of the overall energy required for melting can be provided by means of an economical fuel such as coal by 216270 I thus preheating the batch material to a temperature just below the tesperature at which significant fusing occurs. By feeding a nearly homogeneous mixture of batch and ash to the liquefying stage, the melt that is subsequently formed can be essentially uniform in composition even though substantial quantities of ash have been introduced.

Therefore, one of the problems associated with the use of an ash-producing fuel such as coal is substantially alleviated.

By combusting the fuel while in contact with the batch material and thus avoiding ash entrainment in the exhaust and slag formation on the interior surfaces of the vessel, environmental problems and deterioration of the furnace are avoided, which is desirable for any melting process. But the avoidance of slag runnage into the melt makes the present invention particularly attractive for the melting of glass and the like where compositional homogeneity is important. Even relatively viscous, difficult to homogenize glass such as soda-llme-silica flat glass, for which there are very high standards of optical quality, can be produced by the present invention. It is also an advantage that no agglomeration of the batch is required.

In yet another aspect of the invention, the oxygen supply and temperature at the preheating stage may be controlled so as to produce substantial amounts of carbon monoxide as a product of the combustion of the fuel. The carbon monoxide is passed to a subsequent stage such as the liquefaction stage where it serves as at least part of the fuel for combustion in that stage. In another alternative, the first stage combustion may be incomplete, whereby some of the fuel may be permitted to remain uncombusted so that it may be passed along with the batch to the second stage to serve as at least part of the fuel there. 2 16270 To permit the use of higher temperatures in the preheating stage and to increase the amount of carbon monoxide produced, the constituents of glass batch that fuse at relatively low temperatures may be omitted from the first stage and Introduced at the second stage or a subsequent stage. Excluding the sodium source (e.g. soda ash) from a soda-liae-silica glass batch permits the use of temperatures in the first stage that are sufficiently high to calcine carbonate source materials such as limestone and dolomite as well as to produce carbon monoxide. Treating the silica source material (sand) alone In the first stage enables the first stage to operate at very high temperatures that can yield large amounts of carbon monoxide exhaust.

Following the liquefaction stage, a subsequent third stage may be provided In which the melting process may be carried further. When fuel Is mixed with Che batch, there may be incomplete contact between the fuel and the oxidant in the liquefaction stage, or there may be excess fuel present, and thus the liquefied material may exit the second stage in a reduced state. In that case, the third stage may also include means to re-oxidize the melt, for example, by means of submerged combustion with an oxygen-rich flame and/or by bubbling an oxidizing agent (preferably oxygen) through the melt. Re-oxidizing is particularly useful for avoiding discoloration of clear glass. Undesired coloration of clear glass by iron and sulfide ions can be avoided by re-oxidizing the melt in the third stage.

The chemical constituents of coal ash are generally compatible with those for most glasses, and therefore the glasses can incorporate some of the ash with little or no detrimental affect on the glass product, provided that the ash can be thoroughly homogenized in the melt. However, the amount of ash produced when coal constitutes the 216270 major fuel source for a conventional melting process is difficult to adequately homogenize for some types of glass for which optical requirements are critical. Therefore, It is an advantage of the present Invention that coal is employed as the fuel in a discrete stage of the overall melting process so that mixing of the batch with the ash is provided prior to liquefying. Also, in the discrete preheating stage less than the total energy requirement need be provided so that less coal is required and less ash is produced. Moreover, the overall efficiency of Che staged melting process has been found to reduce the overall energy requirements for melting glass, further reducing fuel requirements. As a result, coal may constitute a major portion or Che entire energy source for preheating even flat glass batch up to the fusion Cemperature. In some modes of operation the coal may constitute the major or entire energy source for the entire liquefying operation.

The novel fuel arrangements of Che present invention may constitute the entire fuel source or may supplement conventional heat sources. The portion of Che total thermal energy requirement of the preheating stage contributed by the novel arrangements is substantial; that Is, greater than that provided by prior art inclusion of carbonaceous material as a melting aid, coloring agent, or binder. It is believed that contributing as much as 5 percent of the energy is uncharacteristic of these prior art uses of carbonaceous materials in a melter. For economic reasons, it is preferred that the novel fuel usage of the present invention be maximized so that it supplies a majority of the energy through the preheating stage, and optimally all of the energy.

Another feature of preferred embodiments of the present invention Is the suppression of exhaust emissions of products of 2 16270 Incomplete combustion such as smoke, soot, or substances volatilized from the fuel. As batch material in contact with solid or liquid fuel is conveyed tovard a heated zone, the temperature of the fuel gradually increases and the fuel begins to give off volatlles and to smolder before being fully ignited. The resulting objectionable emissions are substantially eliminated by this aspect of the present Invention by maintaining the flow of gas in the preheating stage in generally the same direction as the conveyance of the batch-fuel mixture through the preheating stage. This co-current flow pattern carries the emissions from the early stages of heating into the combustion zone, where the combustible emissions are incinerated. Not only are the objectionable emissions eliminated, but also their combustion contributes to the heating of the batch materials. The exhaust gas from the preheating stage may be subjected to further combustion by passing it to a subsequent combustion zone such as in the liquefying stage.

Other environmental advantages also result from the invention. The stagewlse approach lends itself to the use of oxygen Instead of air to support combuscion. The elimination or reduction of the amount of nitrogen in the combustion gases reduces the amount of nitric oxides (NO^) produced. Exhaust gas volumes are considerably reduced when using oxygen firing, thereby reducing gas velocity, which in turn yields less entrainment of particulate batch material. The absence of nitrogen also produces a higher flame temperature. The use of essentially pure oxygen and the exclusion of all air maximizes these advantages, but the advantages can be partially realized in accordance with the degree to which the oxygen concentration exceeds that of air.

Another environmental advantage is that some of the sulfurous emissions usually associated with the combustion of sulfur-containing 216270 fuels such as coal may be suppressed. Contact between the combustion gases and the batch material (particularly glass batch containing limestone or the like) may remove sulfur oxides from the gas stream.

In an alternative approach within the broader aspects of the present invention, fuel that may have an ash content Is combusted at a stage of the melting process devoted to initially liquefying the batch material, so that any slag that forms from the ash content of the fuel becomes integrated into the liquefying material. Since the slag is Incorporated into the product stream at an early stage of the melting process it can be subjected to homogeni2ation at that stage and in subsequent stages of the melting process.

Preferred embodiments of the liquefaction stage entail sloped melting surfaces encircling a central cavity, whereby a large portion of the vessel interior surface area constitutes melting material upon which the ash or slag may be trapped. Batch is fed onto the sloped surface as liquefied material flows down the sloped surface to a drain. In a subsequent stage the melting process may be furthered. The relatively small amount of refractory exposed to slag in the liquefaction stage reduces the potential for erosion of the vessel and concentrated runnage of slag into the melt.

The batch material and the coal or other solid or liquid fuel are preferably in contact with each other as the fuel is combusted in the liquefaction stage. The fuel and batch may be fed separately, but it is preferred to mix the fuel with the batch prior to feeding. Once the liquefaction zone is heated to the ignition point of the fuel, combustion of the fuel is sustained by supplying an oxidizing agent, preferably substantially pure oxygen, to the zone of combustion. 2 1 62 In an alternative embodiment, a burner of a known type for burning powdered solid fuels such as coal may be utilized in the liquefaction stage. Any gas-entrained ash is collected on the encircling melting surfaces and becomes integrated into the liquefied batch material.

The Invention will be more fully understood from the drawings and the description which follows.

The Drawings FIG. 1 shows a preferred embodiment of the present Invention including a rotary kiln preheating stage shown partially broken away, a rotary second stage liquefaction chamber, and a third stage refining chamber.

FIG. 2 Is an enlarged vertical cross-sectional view of the second and third stages wherein the third stage is provided with submerged combustion means.

Detailed Description The detailed description of the Invention is made with reference to an example of a glass melting operation for which the invention has been found to be particularly useful. The invention is useful with all types of glass, including flat glass, container glass, fiber glass, and sodium silicate glass.

However, It should be understood that the invention is applicable to the melting of other, similar materials and in particular to the conversion of mineral-type materials to a molten state. Other examples include: fusing of glassy and ceramic materials, melting of frits, and smelting of ores. 216270 The first stage may take the form of a variety of gas/solid contact devices, but the preferred embodiment is a rotary kiln 1 as shown in FIG. 1. Alternative devices include a fluidized bed and a cyclonic separator/contactor as are known in the art. The rotary kiln comprises a cylindrical shell 2 rotatably supported on rolls 3 at a slight angle from horizontal. A single-walled metal shell as shown in the drawing may be adequate, or better thermal efficiency may be attained by means of a refractory lining or a double walled metal shell with insulation between the walls.

A stationary Inlet housing 4 closes the inlet end of the rotary kiln. Feed duct 5 extends through the housing wall for directing pulverulent batch material into the rotary kiln from a feed rate control device 6. The batch B may be mixed with fuel prior to being fed to the rotary kiln, or fuel and batch may be fed separately to the rotary kiln where they become mixed. Oxidizing gas (e.g., air, but preferably oxygen) may be fed to the rotary kiln by a conduit 7 extending through the wall of inlet housing 4. The conduit 7 may project into the rotary kiln a sufficient distance to establish the combustion zone some distance downstream from the batch feed area. Batch materials that include oxygen-containing compounds such as carbonates may contribute some of the oxygen for supporting the combustion. This is advantageous because carbon dioxide is removed before the batch is liquefied. After liquefying, release of the carbon dioxide would have produced bubbles in the melt that are difficult to eliminate. In the preferred embodiment the products of combustion flow cocurrently with the batch through the rotary kiln into the second stage liquefying means 10 by way of an outlet enclosure 36 that joins the two stages. 216270 Ignition nay be Initiated In Che combustion zone by auxiliary heating means such as a burner temporarily inserted Into the kiln. Once ignition of the fuel In contact with the batch is established, the combustion zone can be maintained at a substantially fixed region of the rotary kiln by balancing the oxygen feed rate and the rate at which the batch and fuel are conveyed along che rotary kiln. The lacter rate Is essentially controlled by the speed with which che inclined kiln is rotated. The solid materials and the gas streams move cocurrently through the rotary kiln so that volatile materials initially driven from the fuel are carried into the combustion zone where they are incineraced.

AlChough not preferred, gas and bacch could flow countercurrent to each other In Che rocary kiln or other preheater. In that case, it may be necessary to provide means Co render the exhaust environmentally acceptable, such as a bag collector for partlculaces. A porClon of the exhaust may be recycled to a combustion zone in either che preheater or the liquefaction stage so as Co eliminate combusCibles. Another technique to treat che exhausc gas and Co recover waste heat Is Co pass the exhaust inco contact with the bacch macerlal in an addlclonal, preliminary preheacing stage. A bacch mixture chat includes carbonaces (e.g., limestone) is also useful in stripping sulfur oxides from che exhausc.

The specific preferred embodimenC of che second scage 10 is shown in FIG. 2 and is in accordance with the Ceachlngs of U.S. Patent No. 4,381,934 of Kunkle et al. and of U.S. Patent Specification No. 4559071 also of Kunkle et al., the teachings of which are hereby incorporated by reference. The second stage is adapted to liquefy the batch and is characterized by a sloped melting surface to receive batch materials that melt as a chin layer on che sloped surface . ^ t i J - , : o : ;« t0JULl987£ ... * /• 216270 and quickly drain Eherefrom when liquefied. The liquefaction stage 10 shown here is a preferred embodiment of che Kunkle et al. teachings wherein the sloped surface substantially encircles a central cavity and the vessel rotates about a substantially vertical axis. The circular arrangement offers distinct advantages for the present invention and for the efficiency of the melting process in general, but it should be understood that the present invention in its broader aspects is not limited to the circular liquefaction arrangement.

By separating the liquefaction step from the remainder of the melting process, energy is employed more efficiently in each stage of the process by optimizing the conditions in each stage to meet the particular needa of the step being performed there. Additional efficiencies are achieved by encircling the heated zone with the batch material and by employing an insulating layer of the batch material or a compatible substance to thermally insulate the liquefaction zone. Because of the overall energy efficiency of the stagewlse process, and because only a portion of the overall energy requirement for melting is consumed in the liquefaction zone, it has been found that the amount of energy consumed in the liquefaction stage is relatively low and a variety of heat sources can be used efficiently. Combustion of fuel, particularly with oxygen firing, is preferred, and electrical sources such as electric arc or plasma torch may be used. Coal or other solid fuel may constitute a portion or all of the fuel in the second stage, some of which may be unburned fuel from the first stage. When carbon monoxide is produced in the first stage, the exhaust from the first stage may be passed to the second stage where it may supply a substantial portion of the energy requirement there. 2 162 With reference to FIG. 2, the liquefaction stage 10 includes a generally cylindrical vessel 12 which may consist of a steel drum. The vessel 12 is supported on a circular frame 14 which is. in turn, mounted for rotation about a generally vertical axis corresponding to the center line, or axis of symmetry, of the vessel on a plurality of support rollers 16 and aligning rollers 18. A bottom section 20 of the vessel holds an axially aligned annular bushing 22 defining a central drain opening 24. The bushing 22 may be comprised of a plurality of ceramic pieces, and the bottom section 20 may be detachably secured to the remainder of the vessel 12 so as to facilitate changing the bushing 22.

A refractory lid 26, preferably in the configuration of an upward dome, is provided with stationary support by way of a surrounding frame member 28. The lid 26 may include at least one opening through which may be extended at least one cooled gas supply conduit 30. The supply conduit 30 may constitute a burner or merely a supply conduit for oxygen or other oxidizing agent to support combustion of the fuel being supplied to the liquefaction chamber. If fuel is being supplied from the first stage, the conduit 30 may be used to supply oxygen or the like to the vessel after the ignition temperature has been achieved. Optionally, a portion of the heat for the liquefaction stage may be supplied by a conventional burner or other heat source in addition to the energy being provided by fuel from the first stage. The conduit 30 may be centralLy located as shown to flood the entire cavity with oxygen, or it may be angled or located off-center to direct the oxygen and/or fuel onto the melting layer.

An opening 32 through the lid 26 may be provided for feeding the batch to the liquefaction stage, and, as shown in FIG. 2, an outlet enclosure 36 at the end of the rotary kiln 1 may be provided with a chute 2 J 62 portion adapted to direct material into the liquefaction stage. An adjustable baffle 38 may be provided at the end of the chute to direct th« flow of batch onto the sidewalls of the vessel 12.

Preferably, a stable layer of pulverulent material 40 lines the Interior of the vessel 12. This layer acts as the insulating lining to protect the vessel 12 from the heat vithin che vessel. In those applications where it is desired to avoid contamination of the product material, the layer 40 is preferably of substantially che sane composition as the batch material. Before the melting process is started, the stable lining 40 is provided in the melter by feeding loose pulverulent material such as the batch material into the vessel 12 while the vessel is rotated. The loose material assumes a generally parabolic contour as shown In FIG. 2. The pulverulent material may be wetted, for example, with water during the Initial stage of forming the stable lining to facilitate cohesion of the layer along the sidewalls. When the lining 40 is comprised of batch material, it need not Include che fuel component Chat may be mixed wich the batch during operation. Other minor differences between the lining material and the throughput material may be acceptable, depending upon the requirements of the particular process.

During the melting process, continuous feeding of batch to the liquefaction stage 10 results in a falling stream of batch that becomes distributed over the face of the stable lining 40, and by the action of the heat from combustion within the vessel 12 becomes liquefied in a transient layer 42 that runs to the bottom of the vessel and passes through the open center 24 in the bushing 22. The liquefied material 44 falls from the first stage 10 into the second stage 11 for further processing. In this manner, the initial step of liquefying the batch can be efficiently carried out because the material, once it has become 216270 liquefied, immediately is removed from the vicinity of the heat source and is continuously replenished with fresh batch material, thereby maintaining a large temperature difference and therefore a high rate of heat transfer in the liquefaction vessel. The constant replenishment with relatively cool, fresh batch in cooperation with the Insulating lining serves to preserve the structural Integrity of the liquefaction vessel without the use of forced cooling of the vessel.

The material for the lining 40 provides thermal insulation and preferably also serves as a non-contaminating contact surface for the transient melting layer 42 and, most preferably, the stable lining includes one or more constituents of the batch material. It Is desirable for the thermal conductivity of the material employed as the lining to be relatively low so that practical thicknesses of the layer may be employed while avoiding the need for wasteful forced cooling of the vessel exterior. In general, granular or pulverulent mineral source raw materials provide good thermal insulation, but in some cases it may be possible to use an intermediate or product of the melting process as a non-contaminating, stable layer. For example, in a glassmaking process pulverized cullet (scrap glass) could constitute the stable layer, although a thicker layer may be required due to the higher thermal conductivity of glass as compared to glass batch. In metallurgical processes, on the other hand, using a metallic product as the stable layer would entail unduly large thicknesses to provide thermal protection to the vessel, but some ore materials may be satisfactory as insulating layers.

The preferred embodiment of the liquefaction stage described above entails rotating the lining about the central cavity, but it should be understood that the present invention is applicable to embodiments In - L5 - 216270 uhlch che lining encircles che heaCed cavity but is not rotated. Additionally, the invention is applicable to embodiments in which the lining is a sloped surface, but does not encircle the heac source (e.g., melting takes place on a ramp). Examples of such variations are described in the aforesaid Kunkle ec al. patent specifications.

Air could be used as the oxidant, but it Is preferred to use oxygen (I.e., a higher concentration of oxygen than in air) so as to reduce the volume of gaseous throughput. As a result, the equipment in both first and second stages may be made compact since the exhaust gas stream is relatively low in volume and high In temperature. Also, eliminating nitrogen from the system Increases che emissivity of the flame and therefore increases heat transfer. TTie intense heat of combustion supported by oxygen firing Is compatible with che preferred embodiments of the second stage because of the thermal protection and efficient heat transfer afforded by the encircling lining.

The temperature attained in the preheating stage depends upon the amount of combustion! which in turn depends upon the amounts of fuel and oxygen provided. Even a small amount of combuscion is useful for the sake of che heat it transfers to the batch materials. Preferably, the amount of heat generated by the combustion in the first stage is enough to produce a maximum temperature increase of the batch without fusing batch ingredients to the extent that the batch is no longer free-flowing. For example, a typical flat glass batch mixture containing substantial amounts of soda ash would be essentially restricted to temperatures below the melting point of soda ash (SSl'C), preferably lower, to avoid clogging of the rotary kiln. In one option, the relatively low temperature melting ingredients of the batch may be omitted from the batch being fed to the first stage, but may be fed ^ 1 fc <V - 16 - ' 0 i ' JUL 1987? l directly to che second stage, thereby permitting higher temperatures to be attained in the first stage. Advantageously, at temperatures above about 870eC calcium carbonate and magnesium carbonate, typical ingredients of a glass bacch, are calcined, i.e., they decompose and release carbon dioxide. Eliminating the carbon dioxide while che materials are still in the solid state is advantageous because it avoids production of carbon dioxide bubbles in the melt. Even higher temperatures can be permitted in the preheater if the material being heated in that stage is restricted to the highest temperature melting portions of the batch and Che remainder of che ingredients are fed directly to a downstream scage. For example, heating only sand in the rotary kiln would permit preheat temperatures in excess of 1000°C to be attained. Separate preheating facilities may be provided for any of the materials that bypass the first stage. Some of the glass batch Ingredients such as soda ash or caustic soda may be fed to the second stage in molten form. It may also be preferred to feed cullet directly to the second stage when the first stage is operated at relatively high temperatures, in which case che cullet may be preheated by contact with exhaust gas.

At most operating temperatures the first stage combustion can produce some carbon monoxide if insufficient oxygen is provided to complete combustion of the fuel. Thus, the exhaust from the first stage can be passed to the second stage where the carbon monoxide content serves as part or all of the fuel for the second stage when combusted with additional oxygen. The proportion of carbon monoxide in the products of combustion increases and the proportion of carbon dioxide decreases at higher temperatures. Therefore, to produce predominating proportions of carbon monoxide to fuel the second stage, it is preferred 2 1627 that the first stage be operated at a peak temperature greater than about 900°C. When supplied with sufficient fuel and a deficiency of oxygen, the entire fuel requirement for the second stage can be supplied by carbon monoxide from the first stage. Combustion of fuel to carbon monoxide releases approximately one third of the heat content of the fuel, che remainder being released upon combustion of the carbon monoxide to carbon dioxide. Therefore, the relative energy requirements of the first and second stages should be taken into account when selecting the amount of carbon monoxide to be produced in the first stage. For example, glass batch is capable of utilizing twice as much energy in che preheaclng scage as in the liquefying scage, so thac producing only carbon dioxide in the first stage may not be the most efficient use of the energy. When preheating a complete flat glass batch mixture, a preferred distribution of the heat content of the fuel can be achieved at an output from the first stage of approximately 50% carbon monoxide and 50Z carbon dioxide (molar basis).

The ability to employ coal is an advantage of the present invention because of the abundant supply and relative low cost of coal in some regions. But other solid or liquid carbonaceous fuel materials may be used to advantage In the present invention, for example, fuel oil, coke fines, petroleum coke, peat, and lignite, oil shale, sawdust, bagasse, and paper waste. Liquid petroleum products such as fuel oil also have the advantage of wetting the batch so as to suppress dust formation and entrainment in the exhaust gas stream.

For economic reasons, coal is the preferred fuel, in particular, bituminous coal. The heating value of a typical Pennsylvania bituminous coal is generally in the range of 11,000 to 15,000 BTU per pound (25.5 million to 34.8 million joules per kilogram) with an ash 2 16270 content ranging from about 3 percent to 9 percent by weight depending upon the source. To melt glass In a conventional, efficiently operated, overhead fired regenerative furnace burning natural gas or fuel oil is generally considered to consume at least about 6 million to 7 million BTU per ton (7 million to 8 million joules per kilogram) of glass produced. Taking a typical Pennsylvania coal as an example, with a heat value of about 13,800 BTU per pound (32 million joules per kilogram) and an ash content of about 7 percent by weight, combustion of such a coal in a conventional glass melting furnace to meet the entire energy requirements of melting would yield an unacceptably large amount of ash. The liquefaction process described above has been found to consume from about 2 million to about 3 million BTU's per ton (2.3 million to 3.5 million joules per kilogram) of throughput. At that level of energy consumption, much less coal is required to supply the energy needs, and therefore the ash introduced into the melt from che coal is at acceptable levels even for producing glass of the high quality level required for flat glass.

The amount of coal to be uClllzed will depend upon the temperature to be achieved in the preheating stage and the heat content of the particular coal, which in turn is a function of its fixed carbon pontent. Because combustion may not be complete due to inaccessibility of oxygen to all parts of the coal, adding slightly more coal than is theoretically required may be preferred. By way of example, about 2% to 3Z by weight of the Pennsylvania coal described above mixed with a flat glass batch mixture has been found to preheat the batch to about 550°C to 650°C when combusted with excess oxygen. The amount of carbon monoxide produced in such a case is small. In another example, a flat glass batch with the soda source (e.g., soda ash) omitted from the first stage (thus comprised chiefly of sand, limestone, and dolomite), having about 6% to 216270 10Z by weight of coal mixed therewith. Is preheated to about 1100eC to 1300"C when combusted. A substantial amount of the limestone and dolomite are calcined, and if a limited amount of oxygen is supplied to che combustion zone, carbon monoxide predominates over carbon dioxide in the combustion produce stream. Ocher carbonaceous fuel materials may be substituted for coal in amounts determined by their respective heac contents. bacch advancageously provides ac lease che majority, and preferably all, of the energy required for the preheating scage, che advancages of Che presenC invention can be obtained by degrees with lesser amouncs of fuel fed with Che bacch. In such a case, some of the energy may be provided by conventional burner means heating the preheating stage. In embodiments where che gas flow is councercurrenc to bacch flow in the preheaCer, exhausc gas passed from Che liquefaccion stage Co Che preheacer may provide some energy for preheaclng. preferably finely divided. The coal for example, is preferably no coarser Chan 60 mesh (US standard sieve size) and 200 mesh coal has been found to be particularly satisfactory. The lgnicion point of coal varies somewhaC, but oxidation of a typical bituminous coal may begin at about 170°C, and combustion is generally self-sustaining at temperatures above 250°C when supplied with pure oxygen.

The following is a typical ash content from 25 parts by weight of coal: IC should be understood chat while Che fuel in contacC with the The solid fuels such as coal Co be mixed wich the batch are SiO 2 1.2 parts by weight 0.6 0.27 2 162 70| CaO 0.1 Na and K 0.5 Ic can be seen chac these ash consdcuencs are compatible with che composition of soda-lime-silica flat glass which may have che following composition: Si02 72-74 Z by weighc A1203 0-2 -s, Na,0 12-15 * * ^ K20 0-1 MgO 3-5 CaO 8-10 F«203 0-0.2 S03 0-0.5 Soda-lime-sillca glass of the above type usually has a viscosity of at lease 100 poises at a temperature of 1425°C.

The temperaCure at which the batch liquefies in the second stage will depend upon Che particular batch materials, especially Che amount and melting temperature of its lowest melting temperature ingredients. With glass batch, the most common low temperature melting ingredient is soda ash which melts at 1564° F. (851° C.). In practice, it has been found that commercial flat glass batch formulas liquefy at a v somewhat higher temperature, about 2,000® F. (1090° C.) to about 2100° F. (1150° C.). Heat within the liquefaction stage may raise the temperature of the liquefied material slightly higher before it drains from the stage, and thus liquefied glass batch flowing from the liquefaction stage 10 may typically have a temperature on the order of about 2300° F. (1260° 216270 C.) but usually no higher than 2400°F (1320°C). Such a temperature and the short residence time In the liquefaction vessel are seldom adequate to fully complete the complex chemical and physical reactions involved in che melclng process. Accordingly, che liquefied macerlal is transferred to a third or "refining" stage 11 in which the melting process is furthered.

For glass, treatment in the refining zone typically entails raising the temperature of che liquefied macerlal co facilitate melting of residual sand grains and Co drive gaseous inclusions from Che melt. A peak temperature of about 2500" F. (1370" C.) to abouC 2800® F. (1510* C.) is considered desirable for refining flat glass. Anocher desirable operation that may be carried out in this sCage is to homogenize the molten macerlal by agication. Also, when the batch is liquefied under reducing conditions, resulting in the molten material entering the refining stage in a reduced condlcion, re-oxidacion of the melt may be required for some end uses. Therefore, a function of the refining stage in the present Invention can be the introduction of an oxidizing agent into the melt. All of these objectives are achieved by the preferred embodiment shown in FIG. 2. The vigorously scirred refining stage is well adapted not only for adjusting the oxidation state of the melt, but also for adding colorants, cullet, or compositional modifiers that are relatively easily melted. Great flexibility for making a wide variety of products is thus provided.

The preferred embodiment of the refining stage as shown in FIG. 2 employs submerged combustion in two chambers. A single-chambered refining stage may suffice for some applications, but for flat glass the preferred embodiment entails two submerged combustion chambers 50 and 52, each retaining a pool 53 and 54, respectively, of the molten material. 216270 The chambers may be provided with oxygen bubbler Cubes 55 and 56 and vaCer-cooled burner.- 57 and 58 below che level of che molCen material. A submerged chroac 59 permits macerlal Co flow from chamber 50 inco chamber 52. An opening 60 ac che Cop of chamber 50 pennies che molten maCerial 44 Co fall from the liquefaction scage 10 inCo che chamber 50. Exhausc from Che liquefier 10 and the first scage 1 may encer the refiner through an opening 60. An exhausc opening (noc shown) may be provided in the upper portion of chamber 50. In chamber 52 an opening 62 is provided in che upper portion thereof for the escape of exhausc gases.

Fuel such as natural gas and an oxidant, preferably oxygen, are fed Co che burners 57 and 58 and combuscion occurs as che gas streams enter Che molten pools 53 and 54. Another fuel which may be used Co advancage in the submerged combuscion burners is hydrogen because iCs produce of combuscion is wacer, which is highly soluble in molten glass. Employing oxygen as the oxidant is advantageous because it avoids introducing into the melt the major nitrogen constituent of air, which has poor solubility in molten glass. Using undiluted oxygen also improves contact between the oxygen and che reduced species in che melc. An excess of the oxidant may be provided to the burners beyond that required for combustion of the fuel so as to correct the reduced condition of the liquefied material entering the refining stage. AlCernatively, if the liquefied material entering the refining stage includes a sufficient amount of uncombusted carbon, or if the temperature of the melt need not be increased, the oxidant alone may be injected into the molten pools 53 and 54 so as to provide the re-oxidizing function only. The oxidant may be introduced separately from the submerged combustion burners, such as through bubbler tubes 55 and 56. It has been found advantageous to use bubblers In combination with submerged 2 J 62 70 combustion. The bubblers can be adapted to inject a stream of small bubbles of oxidant into the melt, which enhances the surface area of contact between the melt and the oxidant gas, and Che submerged combustion provides vigorous agitation to mix the oxidant bubbles throughout the molten mass. The submerged combustion also provides very effective homogenizetion of the melt.

The amount of excess oxidant to be supplied to the refining stage will vary depending upon the particular condlcions encountered and will depend upon che degree of reduction of che macerlal entering che stage and Che oxidation state desired for the final product. The degree of agitation, the vessel size and configuration, the effectiveness of the gas-llquld contact, and the residence time within the refining stage are factors in achieving re-oxidation. In order to achieve homogeneous re-oxidation to meet Che standards for flat glass, it has been found preferable to carry out the re-oxidation in two sequential chambers as shown in the drawing, thereby providing greater assurance that each portion of the throughput is subject to oxidizing conditions during an adequate residence time. In glass, a reduced condition yields a brown colored glass due to the presence of sulfur in Che sulfide sCaCe and iron. If clear glass is desired, re-oxidation is carried out Co sufficienCly raise the oxidation state of Che coloring ions, typically +3 +2 expressed in terms of the Fe /Fe ratio. For a standard commercial +3 +2 grade of clear float glass the Fe /Fe racio is in the range of about 1.5 to 3.0, with a transmittance of at least 70% (preferably at least 80 %) to light having a wavelength of 380 nanometers at a thickness of 6 millimeters. Clear float glass may sometimes also be characterized by at least 60 percent transmittance at 1000 nanometers (6 millimeter +3 +2 thickness). Fe /Fe ratios considerably greater than the above 216270 have been achieved by bubbling oxygen into molten glass chat was Initially dark brown. The change in coloration from brown to clear upon oxidation Is readily observable, so that che appropriate degree of oxldaclon can be easily esclntaced by visual observacion. Although coal may contribute excess iron to the melt, a clear glass can be obtained by re-oxidizing. But precise spectral matching of standard float glass transmittance may require reducing the amount of Iron thac is usually deliberaCely included in the batch (usually as rouge) for coloration.

Downstream from the re-oxidizing chambers, there may be provided a conditioning chamber 64 as shown in the drawing in which additional residence Clme may be provided for Che escape of gaseous inclusions from che melc and for che melc Co cool Co a cemperacure sulced for subsequent processing. The molten material may enter the conditioning chamber 64 through a submerged throat 66. In the arrangement shown, residence time within the chamber 64 is extended by means of a submerged dam 67 and a skim barrier 68 which establish a tortuous path for the melt stream. The processed molten material may be drawn from the refining stage 11 through a canal 70 which may lead to a forming process or the like, which, in che case of glass, may form the glass into a sheet, fibers, bottles or the like by known means.

In an alternative embodiment, ash-containing fuel is burned in Che llquefaccion scage. A pre-heating stage need not be involved in this embodiment. By separating the liquefaction step from the remainder of the melting process, an environment is provided in which a large portion (subseantially all) of the ash contenC of the fuel may be incorporated into Che product material wichout detrimentally affecting the homogeneity of the product. The rapid flow of liquefied material from the liquefaction stage has a substantial mixing effect, and processing in 216270 subsequent stages preferably subjects the liquefied batch and slag to further homogenlzation. Furthermore, because melting cakes place in a relatively chin layer, fuel mixed with che batch material has good access Co oxygen so chac combuscion is relatively complete. As in the other embodiments, the fuel may be fed to the combustion zone separaCely from Che batch, buc Ic is preferred Co feed a mixture of fuel and batch Co che liquefacdon scage. The use of oxygen-enriched firing is also preferred. Incomplete combuscion of fuel In Che liquefaction sCage resulcs in che molten macerlal encering the refining stage in a reduced condition, which may need to be corrected. Therefore, a funccion of che refining scage in this embodimenc is to inCroduce an oxidizing agenc Inco Che melt.

The amount of coal to be utilized in the liquefaction zone will, of course, depend upon the heat content of the particular coal, which in turn is a function of its fixed carbon content. With the Pennsylvania coal described above, adding coal in an amount equal to about six percent by weight of the batch should theoretically provide the total energy required for the liquefaction of flac glass bacch. BuC because combustion is not complete due to Inaccessibility of oxygen to all parts of the coal, adding slightly more coal than is theoretically required is preferred if coal Is to supply the cocal energy requirements of the liquefaction stage. Therefore, by way of example, it is preferred to add coal in the amount of about ten percent of the batch weight. Carbonaceous fuel materials other than coal may be added in amounts determined by their respective heat contents. The invention also encompasses supplying less than the total energy requirement of the liquefaction stage by means of the batch carbon content. In such a case, part of the energy may be provided by batch carbon, and the remainder may 2 1 62 be provided by a conventional fuel burner or other heating means in the liquefaction chamber.

In a specific example of the alternative embodiment, using the arrangement shown in Fig. 2 without preheating, a standard commercial float glass batch (but omitting sulfur containing melting aids such as salt cake or gypsum) was mixed with 5Z to 6Z by weight of coal and melted at a rate of about 15 pounds (6.8 kg) per hour. The coal was the sole fuel source in the liquefaction stage, and the liquefied batch was brown and foamy as it entered the refining scage. Each of the two re-oxidizing chambers was provided with a single submerged combustion burner and a single bubbler tube. Each of the submerged combustion burners was supplied with 250 standard cubic feet per hour (7 standard cubic meters per hour) of hydrogen and 130 standard cubic feet per hour (3.6 standard cubic meters per hour) of oxygen. Each of the bubblers was fed 20 standard cubic feet per hour (0.56 standard cubic meters per hour) of oxygen. The volume of molten material in each chamber was between one and two cubic feet (0.28 to 0.56 cubic meters), and the average residence time for an increment of the melt to pass through both chambers was estimated to be about 30 minutes. The temperature in the first chamber was about 2350°F (1290°C), and the temperature in the second chamber was about 2500°F (1370°C). An auxiliary burner (not shown) was provided in the head space of chamber 64 to help collapse foam. The glass draining from the refining stage was clear, nearly bubble-free, and was more oxidized than commercial float glass. The batch mixture used would conventionally yield a glass having an iron content (expressed as Fe^Oj) of about 0.11% by weight. Due to iron contributed by the coal, the glass in the example was found to have 0.16 percent by weight iron. Sulfur from the coal was found to produce glass having 0.063 2 16270 weight percent S0^ without re-oxidizing, and less than 0.01 SO^ with re-oxidizing.

The detailed description of this invention has been set forth In connection with a best mode, but it should be understood that other variations and modifications that would be evident to those of skill in the art may be employed within the spirit and scope of the invention as defined by the claims which follow.

-S

Claims (39)

ib27o UliAl Ub CLAIM IS:

1. A method of melting glass batch or the like In which combustion of an ash-containlng fuel Is employed as a substantial heat source for the process, characterized by utilizing combustion of the ash-containing fuei in contact with the glass batch material to directly heat the glass batch material in a first zone while ash from the combusted fuel is retained in the batch material, mixing the ash with the batch material by agitation as they are passed toward a second zone, and heating the material further in the second zone so as to advance the material to a melted state.

2. The method of claim 1 wherein combustion of the ash-containing fuel takes place in a preheating stage wherein the batch material Is heated to a temperature below Its fusion temperature, and the second zone comprises a liquefying stage in which che batch material is liquefied.

3. The method of claim 2 wherein the fuel is mixed with the batch material before being fed to the preheating stage.

4. The method of claim 2 wherein the ash-containing fuel provides substanClally all of the energy required for the preheating stage.

5. The method of claim 2 wherein the fuel includes coal.

6. The method of claim 2 wherein the fuel Includes a liquid petroleum product. - 29 216270.

7. The method of claim 2 wherein che preheaclng scage Includes agitating the batch materials in a rotating vessel as the batch materials are conveyed from one end of the rotating vessel to the other end. —\

8. The method of claim 2 wherein che batch material is liquefied on a sloped surface in the liquefying scage and drains freely therefrom. rs W1"

9. The mechod of claim 2 wherein an oxygen source having a higher concentration of oxygen than air is fed to the preheating stage to support the combustion.

10. The method of claim 9 wherein the oxygen source consists essentially of oxygen.

11. The mechod of claim 2 wherein che batch macerlal is conveyed ehrough the preheating stage from an inlet end cowards an ouclec end, and che flow of combuscion gases in the preheating stage is mainCained generally in Che direction of the outlet end.

12. The mechod of claim 11 wherein products of combustion from che preheating stage are passed to the liquefying stage.

13. The mechod of claim 12 wherein the products of combustion include carbon monoxide which is burned in the liquefying stage. - 30 - 216270

14. The method of claim 2 wherein the batch material fed to the preheating stage includes alkaline earth carbonates, and the temperature in the preheating stage is sufficient to calcine a substantial portion of the carbonates.

15. The method of claim 14 wherein the material fed to the first stage is substantially free of constituents that melt at temperatures below the calcining temperature, further including feeding to the liquefying stage batch material that melts at temperatures below the calcining temperature. ■N

16. The method of claim 2 wherein the batch material comprises a batch mixture for a soda-lime-silica glass.

17. The method of claim 14 wherein the temperature in the combustion zone of the first stage is at least 900°C.

18. The method of claim 9 wherein the oxygen source is substantially free of nitrogen.

19. The method of claim 2 wherein batch material entering the second stage is deposited onto a sloped surface facing a central heated cavity.

20. The method of claim 2 wherein the batch material is discharged from the preheating stage in a pulverulent, substantially free-flowing condition. - 31 - 216270

21. The mechod of claim 11 wherein a gaseous source of oxygen Is Introduced Into che preheaclng vessel at an Intermediate location spaced from che inlet end and che outlet end.

22. The method of claim 19 wherein the batch material is drained from the second stage Immediately upon liquefying.

23. The method of claim 2 wherein a portion of the oxygen for combustion of the fuel in che preheaclng stage is provided by oxygen-containing compounds in che bacch macerlal.

24.liquefied In che flrsC zone, and combuscion of the ash-contalnlng fuel in the first zone supplies a major portion of che energy required to liquefy the batch material.

25. The method of claim 24 wherein the bacch is a soda-lime-silica glass batch.

26. The method of claim 25 wherein the batch is formulated Co produce a glass having a viscosity of at least 100 poises at 1425°C.

27. The mechod of claim 24 wherein the fuel is mixed with the bacch prior co being fed to the zone in which Che combustion takes place.

28. The method of claim 24 wherein batch maCerial in the first zone is liquefied on a sloped surface encircling a central cavity. 24. The method of claim 1 wherein the batch material Is 32. - 216270

29. The method of claim 24 wherein che liquefied macerlal Is drained from che first zone In a reduced condicion, and Is passed Co a downstream zone where it is subjected to re-oxidizing conditions.

30. The method of claim 24 wherein the fuel In contact with the bacch aacerial constitutes substantially Che entire energy source for liquefying the batch.

31. The method of claim 24 wherein the fuel is coal.

32. The method of claim 29 wherein the oxidizing condition in the second zone Is provided by injecting gaseous oxygen Inco a body of the liquefied material.

33. The mechod of claim 32 wherein aglcacion of che material in the second zone is provided by injection of combusting gases into the body of liquefied material.

34. The method of claim 24 wherein che fuel is a liquid pecroleum product.

35. The mechod of claim 28 wherein che sloped surface is rotated about the central cavity.

36. The method of claim 24 wherein the liquefied material is removed from the first zone in a partially unmelted condition. - 33 - 216270

37. The method of claim 24 wherein Che second zone is divided Inco tvo chaabers and the liquefied material passes from one chamber to Che other with submerged combustion being provided in each chamber.

38. A method as claimed in claim 1 and substantially as herein described with reference to any embodiment.

39. Glass produced by the method of any of the preceding claims. I fcD 7HlsOOn<) DAY OF A. J. PARK & SON PER ^5^ AGENTS FOR THE APPLICANTS - 34 - .