The present invention relates to industrial processes in which an enclosed furnace is operated at elevated temperature. The present invention relates particularly to furnaces for producing glass.
Glass is customarily produced by melting glassmaking materials, by which is meant raw materials such as sand, limestone and soda ash (referred to as “batch”), and recycled pieces of glass (referred to as “cullet”), in a furnace. The glassmaking materials are typically fed at or near one end of the furnace (the “back wall”) to produce a uniform stream of molten glass which can be further processed, for instance by removal of dissolved gases and bubbles (“fining”), and the molten glass leaves the furnace (typically out the “front wall”) to be formed and cooled downstream of the furnace into solid products.
Melting the glassmaking materials requires establishing elevated temperatures in the furnace, to melt solid glassmaking materials and to maintain the molten glassmaking materials in the molten state in the furnace and as they pass through and out of the furnace. The elevated temperature is typically established by combusting fuel at a plurality of burners within the furnace. The fuel can be combusted with air as the source of oxygen, or in what is referred to as “oxy-fuel” combustion the fuel can be with gaseous oxidant having an oxygen content higher than that of air, as described herein.
In a glassmelting furnace the temperature of the crown will typically exhibit a peak at a location in the crown (the “hot spot”) which customarily dictates the maximum operating capacity of the furnace to produce glass, as the maximum furnace production rate is typically limited by the maximum usable crown refractory temperature. Attempts to increase the output of a glassmelting furnace by melting more glass, i.e. by charging more batch and cullet materials into the glass furnace, are believed to require increasing the fuel input to the furnace in order to provide the necessary additional heat and to maintain a proper temperature profile in the molten glass bath. However, as the fuel input is increased to produce more glass, the crown temperature will increase. This is not a practical solution because when increasing the combustion will increase the crown hot spot and because when the crown hot spot temperature is already at or near its maximum that can be tolerated by the crown, the firing rate cannot be increased further near the hot spot without risking damage to the crown. In order to increase the production rate without increasing the temperature at the hot spot, other methods such as electric boosting (direct molten glass electrical heating by submerged electrodes) and batch and cullet preheating are sometimes used. These methods, however, incur high capital costs and high operating costs.
In oxy-fuel fired furnaces and fuel-air fired furnaces the flue port is typically located in the back wall or in the side wall near the back wall, i.e., in the relatively coldest region of the furnace. The reason for locating the flue port in the coldest region of the furnace is to minimize the sensible heat loss of flue gas leaving the furnace. One might expect that additional air-fuel or oxy-fuel burners could be located in that zone to provide the additional heat that is required for melting additional glassmaking material that is fed to the furnace. However, the present inventors have found that when the firing rate in the feed zone is increased with air-fuel or oxy-fuel combustion, the temperature of the flue gas leaving the furnace increases sharply and the energy consumption to produce molten glass increases sharply. In addition, the heat flux from such added burners would be expected to increase the temperature in other regions of the furnace including at the “hot spot” of the crown by the radiative heat exchanges taking place within the furnace. In order to maintain the hot spot temperature below the safe limit, the firing rate near the hot spot has to be reduced. A reduction in the hot the firing rate near the hot spot has to be made up by increasing the firing rate in the feed zone which further increases the flue gas temperature. Furthermore it is generally believed that the proper longitudinal crown temperature profile is essential to produce good quality glass and increasing the charge zone temperature without increasing the hot spot temperature is hitherto considered to adversely affect the glass quality.
Thus, it is to be expected that providing burners in the zone of the glassmelting furnace near the back wall, into which the glassmaking material is fed, is not a practical option to increase the glassmaking capacity of the furnace.
The present inventors have discovered that, contrary to what would be expected, combustion can be provided in the zone near the back wall of the furnace without increasing the hot spot temperature of the crown of the furnace, and permitting increased production of good quality glass from the furnace.
One aspect of this discovery is a method of producing molten glass, comprising
(A) feeding glassmaking material into a glassmelting furnace having a back wall, a front wall, and a pair of side walls facing each other and each extending from the back wall to the front wall, and a crown, wherein the glassmaking material is fed into a feed zone that extends from the back wall up to 30% of the length of the furnace from the back wall toward the front wall,
wherein no burners are located in side walls or at least one oxy-fuel or air-fuel burner is located in each side wall to provide heat to glassmaking material in the furnace by combustion at each of said burners,
wherein said furnace includes a first regenerator and a second regenerator each having a port opening into said feed zone and (i) said first regenerator port is located in one side wall and said second regenerator port is located in the other side wall, and no air-fuel burner is located between either of said regenerator ports and the back wall, and oxy-fuel burners may optionally be present or not present between said regenerator ports and the back wall, or (ii) said first and second regenerator ports are located in the back wall; while
(B) combusting fuel in said furnace at said burners that are present, and
(C) alternately
(1) passing gaseous combustion products from the furnace into and through a cooled first regenerator to heat the first regenerator and cool said gaseous combustion products, and passing a first part of said cooled gaseous combustion products from said first regenerator, and fuel, into a heated second regenerator and, in the second regenerator, reacting the gaseous combustion products and the fuel in an endothermic reaction to form syngas comprising hydrogen and CO, and passing said syngas from the second regenerator into the feed zone and combusting it in the feed zone, and
(2) passing gaseous combustion products from the furnace into and through a cooled second regenerator to heat the second regenerator and cool said gaseous combustion products, and passing a first part of said cooled gaseous combustion products from said second regenerator, and fuel, into a heated first regenerator and, in the first regenerator, reacting the gaseous combustion products and the fuel in an endothermic reaction to form syngas comprising hydrogen and CO, and passing said syngas from the first regenerator into the feed zone and combusting it in the feed zone,
under conditions wherein the combustion in the furnace of the syngas from the first and second regenerators maintains the temperature of the crown in the feed zone at within 100 C of the highest temperature of the crown in the furnace outside of the feed zone.
Another aspect of the present invention is a method of producing molten glass, comprising
(A) feeding glassmaking material into a glassmelting furnace having a back wall, a front wall, and a pair of side walls facing each other and each extending from the back wall to the front wall, and a crown, wherein the glassmaking material is fed into a feed zone that extends from the back wall up to 30% of the length of the furnace from the back wall toward the front wall,
wherein no burners are located in side walls or at least one oxy-fuel or air-fuel burner is located in each side wall to provide heat to glassmaking material in the furnace by combustion at each of said burners,
wherein said furnace includes a first regenerator and a second regenerator each having a port opening into said feed zone and (i) said first regenerator port is located in one side wall and said second regenerator port is located in the other side wall, and no air-fuel burner is located between either of said regenerator ports and the back wall, and oxy-fuel burners may optionally be present or not present between said regenerator ports and the back wall, or (ii) said first and second regenerator ports are located in the back wall; while
(B) combusting fuel in said furnace at said burners that are present, and
(C) alternately
(1) passing gaseous combustion products from the furnace into and through a cooled first regenerator to heat the first regenerator and cool said gaseous combustion products, and passing gaseous reforming reactants into a heated second regenerator and, in the second regenerator, reacting the gaseous reforming reactants and the fuel in an endothermic reaction to form syngas comprising hydrogen and CO, and passing said syngas from the second regenerator into the feed zone and combusting it in the feed zone, and
(2) passing gaseous combustion products from the furnace into and through a cooled second regenerator to heat the second regenerator and cool said gaseous combustion products, and passing gaseous reforming reactants into a heated first regenerator and, in the first regenerator, reacting the gaseous reforming reactants and the fuel in an endothermic reaction to form syngas comprising hydrogen and CO, and passing said syngas from the first regenerator into the feed zone and combusting it in the feed zone,
under conditions wherein the combustion in the furnace of the syngas from the first and second regenerators maintains the temperature of the crown in the feed zone at within 100 C of the highest temperature of the crown in the furnace outside of the feed zone.
In the foregoing embodiments the combustion is preferably carried out under conditions wherein the combustion in the furnace of the syngas from the first and second regenerators maintains the temperature of the crown in the feed zone at within 75 C, and more preferably within 50 C, of the highest temperature of the crown in the furnace outside of the feed zone.
In other preferred embodiments, the thermochemical regenerator ports are located in the back wall and the visible flame length is less than two thirds, or even less than one half, of the longitudinal length of the furnace.
As used herein, “glassmaking materials” comprise any of the following materials, and mixtures thereof: sand (mostly SiO2), soda ash (mostly Na2CO3), limestone (mostly CaCO3 and MgCO3), feldspar, borax (hydrated sodium borate), other oxides, hydroxides and/or silicates of sodium and potassium, which materials are also referred to as “batch”, and glass (such as recycled solid pieces of glass) previously produced by melting and solidifying any of the foregoing, which is also referred to as “cullet”. Glassmaking materials may also include functional additives such as batch oxidizers such as salt cake (sodium sulfate, Na2SO4) and/or niter (sodium nitrate, NaNO3, and/or potassium nitrate, KNO3), and fining agents such as antimony oxides (Sb2O3).
As used herein, “oxy-fuel burner” means a burner through which are fed fuel and oxidant having an oxygen content greater than the oxygen content of air, and preferably having an oxygen content of at least 50 volume percent and preferably at least 80 vol. % oxygen, more preferably at least 90 vol. % oxygen, and even at least 99 vol. % oxygen.
As used herein, “oxy-fuel combustion” means combustion of fuel with oxidant having an oxygen content greater than the oxygen content of air, and preferably having an oxygen content of at least 50 volume percent and preferably at least 80 vol. % oxygen, more preferably at least 90 vol. % oxygen, and even at least 99 vol. % oxygen.
As used herein, “air-fuel burner” means a burner through which are fed fuel and air and includes a regenerative air combustion system that preheat combustion air in regenerators.
As used herein, “air-fuel combustion” means combustion of fuel with air.
Turning first to the glassmaking furnace itself,
The furnace (10) also has at least one material charging entrance (20), typically along the inner surface of back wall (3) or in side walls (4) and/or (5) near back wall (3) for other types of glass furnaces, through which glassmaking material (30) can be fed into the melting zone (11) as seen in
The bottom, back wall, front wall, sides and crown of the furnace should be made from refractory material that can retain its solid structural integrity at the temperatures to which it will be exposed, i.e. typically 1300° C. to 1700° C. Such materials are widely known in the field of construction of high-temperature apparatus. Examples include silica, fused alumina, and AZS.
In the embodiments shown in
When optional burners are installed in melting zone (11) combustion occurs in melting zone (11) as fuel such as natural gas or fuel oil, injected at or near the locations where these ports open into melting zone (11), mixes with hot combustion air or oxidant to form a flame and to generate heat in the melting zone to melt glassmaking material and maintain the glassmaking material in the molten state. Combustion can occur simultaneously at all ports, or as in the case with regenerative burners combustion can occur alternately at some ports and then at some other ports.
Removing gas bubbles from molten glass is an essential requirement in glass melting furnace to produce good quality glass. Molten glass must remain in the furnace for a sufficient time to allow gas bubbles to leave the glass through buoyancy, a process known as fining. In a glass melting furnace the operating condition of the furnace is typically controlled by monitoring crown thermocouples and tank bottom thermocouples. A state-of-the art container glass furnace with high production rate, employing already known operation technique not incorporating the present invention, may operate at a hot spot crown temperature of 1550 to 1600 C located at about two-thirds to three-fourths of the longitudinal length of the furnace from the back wall. Batch materials are charged near the back wall and the crown temperature near the back wall may operate 100 to 200 C below the hot spot temperature or typically at about 1400 to 1450 C. The crown temperature in fining zone (12) near the front wall may operate about 50 C below the hot spot temperature. Batch materials fed from batch charger (20) (
In
This aspect of the overall process proceeds in two cycles, which are referred to herein as the flue cycle and the reforming cycle. These two cycles are performed alternatingly in two or more checker-filled regenerators. This process is preferably carried out in association with oxy-fuel combustion, because the flue gases produced by oxy-fuel combustion have higher H2O and CO2 concentrations, both of which promote the endothermic reforming reactions that are utilized in the method of this invention. When this process is carried out in the cross-fired configuration with air burners (shown in
In the reforming cycle, the RFG/Reforming Fuel mixture enters the second regenerator in which the checker has already been heated, as described herein, and flows through it towards the furnace. The temperature of the RFG/RF mixture passing through the second regenerator continues to increase by extracting heat from the already pre-heated checker. As the RGF/RF mixture passes through the second regenerator, it reaches a temperature at which reforming reactions begin to occur and continue to occur, producing products including H2 and CO. The reforming reactions are endothermic and the heat needed to promote the reforming reactions is absorbed from the heated checker. The gaseous composition that is produced by the reforming reactions typically comprises one or more components such as such as H2, CO, unreacted gases comprising H2O, CO2, CH4, nitrogen, any residual NOx, and soot. The gaseous composition thus produced may also be called “syngas” herein. The syngas emerges from the second regenerator into the furnace and is combusted in the furnace with oxidant to provide thermal energy for heating and/or melting material in the furnace.
After a length of time, the operation of the two regenerators is reversed, i.e., the regenerator that was used in the flue cycle is switched to the reforming cycle, and the regenerator that was used in the reforming cycle is switched to the flue cycle. After a further period of time, the operation of the two regenerators is reversed again. The timing of the reversals can be determined by elapsed time, or by other criteria such as the temperature of the flue gas exiting from the first regenerator that is in flue cycle. The reversal process is carried out according to a predetermined mechanism and plan, wherein valves are sequenced to open and close based on specific timings.
The operation and control of this aspect of the present invention is described below in conjunction with
As shown in
As seen in
As seen in
As seen in
Typically, the heat recovery process proceeds with one regenerator in the flue cycle and one regenerator in the reforming cycle, as seen in
Upon reversal, the flue gas from the furnace passes through regenerator (100), and a portion thereof passes to exhaust (as defined herein) while a portion or the balance is mixed with fuel and the mixture is passed through regenerator (200) and into the furnace. Valve (110) which had been closed is opened, valve (210) is closed, and valve (360) is closed and valve (380) is opened, to permit heated flue gas to pass from regenerator (100) toward and through blower (300), and to permit a portion (303) of this flue gas to pass into regenerator (200) after it is mixed with reforming fuel (230) which enters through valve (220) which had been closed but now is opened. Valve (115) which had been open is closed, and as no combustion aided by oxidant through valve (115) occurs in this phase, and valve (225) is opened. The resulting mixture of reforming fuel and recycled flue gas undergoes in regenerator (200) the endothermic reactions which had occurred in regenerator (100) in the previous cycle as described herein, to produce syngas (425) which passes into furnace (10) where it is combusted with oxidant (235) that is fed through valve (225).
The amount of the flue gas emerging through the regenerator in which it was cooled, that is recycled to the other regenerator for reforming, can be adapted to the particular furnace and the particular characteristics of the flue gas, but it can be said that typically up to about 40% (by volume), and preferably about 6% to 27%, of the flue gas that emerges from the regenerator that is operating in the flue cycle is recycled to be fed into and through the regenerator that is operating in the reforming cycle.
While any ratio of RFG to FG in forming the gas stream that is fed into the regenerator that is operating in the reforming cycle can be utilized effectively in the method of this invention, a preferred ratio of RFG to FG (by volume) is 0.5 to 2.0.
In an alternative embodiment of this invention, RFG fed alternatingly from one of the thermochemical regenerators to the other, can be replaced with a separate reforming reactants stream containing more than 50 vol. % H2O and CO2, including, but not limited to, steam. This embodiment is described with reference to
Referring to
In the embodiment of
The reforming fuel and reforming reactants undergo reforming reactions in each of the heated regenerators to which they are alternatingly fed, and form syngas by endothermic reaction in the heated regenerator, and the syngas is then passed into the furnace and combusted, all as is the case with respect to the embodiments described with respect to
The present invention improves on what had been considered to be established results and limitations in conventional modes of operating a glass furnace.
One critical operating condition of a glass furnace is that the temperatures within the furnace must not be so high that the materials from which the furnace is constructed are damaged. As the temperature within the furnace is typically the highest at the interior surface of the crown, it is beneficial to control operations by controlling the maximum temperature that is reached at the hottest point on the interior surface of the crown (the “hot spot”).
A typical state-of-the art container glass furnace with high production rate may operate at the hot spot crown temperature of 1550 C to 1600 C located at about two-thirds to three-fourths of the longitudinal length of the furnace from the back wall. The temperature in the feed zone (13) is typically 100 C to 200 C less than the hot spot temperature or typically at about 1400 to 1450 C.
To increase the output of a glass furnace by charging more batch and cullet materials into the glass furnace, the fuel input to the furnace has to be increased to maintain a proper molten glass bath temperature profile. But as the fuel input is increased to produce more glass, the crown temperature will increase, and more heat is transferred from the combustion space above the molten glassmaking materials to the incoming feed of glassmaking materials and molten glass, driven by the greater temperature difference between the crown and the molten glass surface. So, when the crown hot spot temperature is already at or near its practical workable maximum, it is not possible to increase the furnace output by increasing the fuel firing rate in a way that would risk increasing the temperature of the crown its hottest spot. In theory one can increase the firing rate of the burner closest to the charge end in feed zone (13) in a cross-fired furnace to increase the heat input without significantly increasing the crown temperature at the hot spot. There are two practical limitations in this approach. First, the maximum firing rate of the burner in the cross-fired furnace is typically limited by the maximum flame length, which is the width of the furnace. When the flame length exceed the width of the furnace, the flue port refractory materials may get damaged by overheating and the flue gas temperature increases, which reduces the heat available within the furnace. Second, carry-over of fine batch materials into flue gas increases when the gas velocity of the flame increases.
It has been thought that additional heat could be provided to the glass furnace by installing and operating oxy-fuel burners or air-fuel burners at the locations designated (100) and (200) in
Without intending to be bound by a particular explanation for these unexpected findings, it is believed that the syngas combustion flame produced under the TCR operation has a significantly higher adiabatic flame temperature than the normal adiabatic flame temperature of ambient temperature natural gas and oxygen combustion, because the syngas from TCR has a higher hydrogen concentration and a high preheat temperature of about 1100 to 1300 C. In the configuration of
In a conventional oxy-fuel fired glass furnace without the TCR aspect of the present invention, when the firing rate is increased, it also increases the flue gas temperature leaving the furnace and the energy consumption to produce molten glass increases sharply. This problem of increasing energy consumption per unit of glass produced is solved by incorporating the (TCR) thermochemical regeneration and combustion process of this invention to efficiently recover the increased waste heat in the flue gas. That is, it has been discovered that TCR has a unique characteristic in that the efficiency of heat recovery increases as the temperature of the flue gas increases. In a conventional air heating regenerator the heat recovery efficiency (% of waste heat recovered as preheat energy transferred to combustion air) remains approximately the same when the flue gas temperature increases. The temperature of the cooled flue gas after the regenerator goes up as the hot flue gas temperature entering the regenerator increases. By contrast, in the TCR heat recovery process employed in the present invention the heat recovery efficiency increases when the flue gas temperature is increased and the temperature of the cooled flue gas after the regenerator increases little as the hot flue gas temperature entering the regenerator increases. The reason for this unique characteristic is believed to be that heat stored in the regenerator is partly recovered through the endothermic chemical reactions that form the syngas. The rate of endothermic chemical reaction becomes significant at above 1500 F and exponentially increases with temperature. When the flue gas temperature entering a TCR regenerator bed (100) or (200) is increased, more heat is stored in the higher temperature zone of the bed and more endothermic reactions occur during the heat recovery cycle to recover the stored heat in the high temperature zone. The resulting hot syngas from the regenerator contains more energy and produces a hotter flame which releases more energy near the feed zone, promoting more rapid melting of charged materials.
This permits the temperature in the feed zone to be increased without increasing the maximum temperature that is exhibited at the hot spot of the furnace.
Thus, the present invention provides an improved furnace operating method to increase the specific production rate of an oxy-fuel fired glass furnace or an air-fuel fired furnace in a cross-fired configuration by increasing the temperature in the feed zone near the back wall by the intense heat from the flame produced by combustion of high temperature preheated syngas and oxygen, without increasing the hot spot temperature while maintaining a good specific energy consumption, by employing the thermochemical regenerator operation described herein and oxy-fuel combustion. In this way, good quality glass can be produce even when the crown temperature profile is flattened (that is, a high crown temperature is maintained over a longer extent of the crown) by increasing the syngas firing rate near the back wall while charging more batch/cullet materials.
This observed phenomenon is shown by computer modeling studies to be consistent with floating batch material over the molten glass in the feed zone of the furnace insulating the molten glass below the floating batch islands from the intense radiation heat from the combustion space above and keeping the molten glass temperature colder than the molten glass temperature near the hot spot. Since the backward circulation flow of the molten glass from the hot spot toward the back wall is driven by the molten glass temperature difference between the hot spot and the back wall, a good backward circulation flow is maintained in spite of a flatter crown temperature profile. As additional relatively cold batch material is charged near the back wall, it cools the molten glass circulating in this zone and helps to maintain a sufficient temperature gradient to produce the required recirculating flow of molten glass from the hot spot of the furnace.
This application claims the benefit of U.S. Provisional Application Ser. No. 62/387,125, filed on Dec. 23, 2015, which is incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/067778 | 12/20/2016 | WO | 00 |
Number | Date | Country | |
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62387125 | Dec 2015 | US |