COMBUSTION OF HALOGENATED HYDROCARBONS WITH HEAT RECOVERY

Abstract: The present invention discloses the disposal of halogenated hydrocarbon waste materials which are burned in a horizontal fire tube boiler (10). In the dis­ closed and illustrated embodiments, liquid and/or gaseous waste of highly chlorinated hydrocarbons are input along with a flow of fuel oil or gas as required to increase combustion temperature. While high com­ bustion temperatures are achieved, a stable flame front is established. A refractory lined combustion chamber (12) of substantial length is incorporated to contain the flame front near adiabatic conditions for sufficient dwell time so that the combustion gases leaving the vicinity achieve near complete combustion. Before entering the water jacket boiler furnace tube (34) the temperature of the flue gas is dropped to a level enabling the use of standard materials of con­ struction of the tube sheets of the boiler, where the fire tube boiler is most vulnerable to corrosion from excessive temperatures and condensation chlorinated hydrocarbons reacting on the interior thereof. The tube sheet boiler permits burning of halogenated hydro­ carbon waste with minimal support fuel requirements to yield flue gas containing exceptionally high hydrogen chloride concentration.

Description: This invention is directed generally to the recovery of heat from the disposal incineration of liquid waste and off-gases, and in particular to those liquid wastes and off-gases containing halogenated hydrocarbons. More specifically, this invention concerns a fire tube boiler system of particular design for achieving efficient incineration of waste feeds containing more highly chlorinated hydrocarbons of lower fuel value than is typically the case. Halogenated hydrocarbon materials are burned in an internally fired horizontal fire tube boiler and the heat of combustion is extracted to produce saturated steam. Halogen values are recovered from the combustion of waste liquids and gases, such as by being absorbed in water. For efficient reclamation of halogen values combustion from highly chlorinated, low fuel value materials should occur at or near adiabatic conditions as possible and at minimal excess oxygen required for combustion. When more highly chlorinated hydrocarbon waste is incinerated, typically which is of lower fuel value, additional fuel feed is neces­ sary for efficient combustion and the combustion temperature is typically higher than is normal for such fire tube boilers. The varying physical and chemical properties of waste feeds, corrosiveness of their combustion products, and the extreme operating temperature required for the effective destruction of toxic substances makes heat recovery a challenging problem. It has been found that commercial packaged steam boilers and incinerators equipped with conven­ tional steam generating heat exchangers have certain deficiencies if fired with liquid waste and off-gases containing halogenated hydrocarbons. The substantially greater heat required for efficient combustion and the excessively corrosive nature of the flue gas generated by combustion have detrimental effect on the structure of boiler apparatus. The tube sheets of tube sheet boilers, when composed of conventional metals such as carbon steel are destroyed by corrosion in a relatively short period of time, requiring exceptionally high maintenance cost for the equipment. Under circumstances where the fire tube boilers incorporate more exotic metals for corrosion resistance, the cost of the boiler itself becomes disadvantageously high. The present invention utilizes commercially packaged fire tube boilers for destruction of halo­ genated hydrocarbons and utilizes conventional end sheet metal material in order that boiler cost will remain as low as possible. The present invention also provides suitable modifications which render standard fire tube boilers efficient for combustion of highly halogenated hydrocarbons. When utilizing commercial fire tube boilers for incineration of highly chlorinated hydrocarbon waste materials it has been found that the volume of the combustion chamber (furnace) is too small to contain the typically larger flame that is needed and to pro­ vide sufficient residence time in the combustion chamber for the combustion of such wastes. Also, these waste materials often have undesirable physical properties to make uniform feed control and atomization of the liquid into fine droplets difficult. As a result, the flame is unstable and is of such length that its contact with the refractory lining and/or metal heat transfer surfaces of the boiler causes failures or significantly reduces the service life of the boiler. It is also known that liquid wastes of highly chlorinated hydrocarbons and off-gases have a high quantity of inert materials and as a result have low caloric values. Firing these waste materials in the water cooled furnace of a packaged fire tube boiler ordinarily requires a high proportion of sup­ port fuel, such as natural gas or fuel oil, to waste feed to maintain a stable flame and sustain combustion for complete destruction of the organic waste. In some cases an incinerator equipped with a conventional steam generating exchanger of the "straight through" variety of the general nature set forth in U.S. Patent 4,198, 384 may be employed to resolve the above problems regarding packaged fire tube boilers, but this type of incinerator also has an inherent problem. Extreme combustion tem­ peratures of 1000°C to 1800°C (12000°C to 1500°C most common in practice) are required to success­ fully destroy toxic substances (to a level required by U.S. government regulations). The front tube section of the straight through exchanger is sub­ ject to rapid failure when directly exposed to the hot combustion gases and the radiant heat from the refractory walls of the furnace. Special designs to reduce the tube sheet temperature and special materials of construction are required for this system to be successful. Obviously, special designs and exotic materials significantly increase the cost of straight through incinerators of this character and therefore render them commercially undesirable. The present invention utilizes the advantages of a refractory lined furnace and also employs a large water cooled furnace interconnected with a fire tube boiler to reduce the combustion gas temperature in the boiler to a level sufficiently low (1000°C or so) that standard materials of construction and design may be employed for the tube sheets of the steam generator, thereby resulting in an incinerator con­ struction of reasonable cost and efficient service­ ability. Very useful fire tube boiler structures are set forth in U.S. Patents 4,125,593, 4,195, 569 and 4,476,791. Halogenated hydrocarbon materials from a waste feed can be routinely combusted in these fire tube boiler structures. The present disclosure sets forth an improvement to such fire tube boiler systems wherein more highly chlorinated hydrocarbons of lower fuel value can be efficiently combusted for HCl recovery and steam generation through the use of standard boiler materials that are not diminished by the excessive corrosion that ordinarily occurs. Thus, this present combustion chamber and fire tube boiler asssembly which enables the incidental recovery of heat resulting from incineration of either liquid or gas waste materials (typically halogenated hydrocarbons) is all accomplished in a satisfactory manner for such disposal. With these above problems in mind, the pre­ sent invention concerns a halogenated hydrocarbon incinerator wherein heat is extracted from an irregular and varied feed of highly halogenated liquid or gaseous hydrocarbon waste which may have minimal caloric value, thereby enabling a water cooled horizontal fire tube boiler to form halogen acids and saturated steam. Internal corrosion of the metal surfaces in contact with the hot combustion gases is avoided by controlling the temperature of the saturated steam produced by the boiler. The corrosive effect of gas in contact with the internal or working surfaces of the incinerator, especially the tube sheets in thus minimized. The incinerator of this invention provides more residence dwell time of waste material in the combustion chamber to ensure that the waste material is completely incin­ erated within the length of the chamber. Also the structure of the combustion chamber is such as to develop efficient burning of waste materials with minimal support fuel producing a flue gas of higher chlorine concentration (HCl). The combustion chamber is also designed to ensure that the tube sheets, which are constructed or ordinary tube sheet material, are subjected to flue gas temperature in the range of about 50 percent of that typically occurring when wastes of this character are incinerated. In light of the vari­ ations in physical properties of the waste materials and irregular atomization, the flame is typically unstable in temperature, size and location. The improved structure of this invention successfully contains a flame front which moves, which flame may extend so far into a conventional boiler as to other­ wise damage refractory lining and/or metal heat trans­ fer surfaces and tube support sheets. More specifically, the present apparatus is described as an improvement in a water-cooled, hori­ zontal fire tube boiler having; (a) a boiler section having a generally closed shell having a vertically disposed metal tube sheet at each end, said shell holding water between said ends, a combustion chamber extending along the length thereof, and within, said shell, and communicating through said tube sheets, a plurality of relatively small metal return-tubes extending the length of, and within the boiler shell and communicating through said tube sheets, the com­ bustion chamber and the return-tubes being in spaced horizontal relationship, and said boiler section defines a folded multi-segment flue gas discharge path therethrough; (b) two end section means, at least one of which is affixed; (c) said shell and said end sec­ tion means having surfaces, except for the tube sheet surfaces, which are exposed to the combustion gases when the boiler is in operation, made of corrosion resistant material or covered with an amount of insulation predetermined to maintain the temper­ ature of such surfaces within a predetermined temper­ ature range during operation; (d) a front end nozzle section adjacent to the combustion chamber; (e) a means for supplying water into said shell; (f) a means for removing steam from said shell; and (g) flue means for removing combustion gases from one of the end sections; the improvement comprising: (h) two combustion chambers wherein: (i) the primary combustion chamber has a front end nozzle section adjacent to the confined primary combustion chamber for containing combustion gases; (ii) said primary combustion chamber communicating with a secondary combustion chamber and into said return-tubes; (iii) said front end nozzle section having feed means for feeding air, supplemental fuel, and halogenated hydro­ carbons into a burner nozzle, within the primary com­ bustion chamber; (iv) means for blowing air past said nozzle to define a flame front having a temperature in the range from 1,000 to 1,800 °C to combust halogenated hydrocarbons; (v) said primary combustion chamber having an elongate extent sufficient to enclose therein the flame front, and wherein said primary combustion chamber terminates opposite said burner nozzle in an aligned and streamlined relation therewith, insulation covered wall means defining an outlet directing flue gas flow from said primary combustion chamber into said secondary combustion chamber; (vi) said secondary combustion chamber is relatively long and extending along the length of, and within, said shell, and communicating through the tube sheets; (vii) the outlet directing flue gas flow being sufficiently spaced from the flame front and sufficiently long that flue gas temperature at the end of said secondary combustion chamber is less than 1,000°C at entry into the folded multi-segment flue gas discharge path; and (viii) an end section means having a confined space for containing combustion gases, said space communicating with said secondary combustion chamber and said return-tubes and defining a portion of said folded multi-segment flue gas discharge path. A further embodiment can be described as an improvement in a water-cooled horizontal fire tube boiler for incineration of waste materials which contain highly chlorinated hydrocarbons, having: (a) boiler means having a water coolant chamber and carbon steel tube sheets supporting a plurality of water cooled gas flow tubes; (b) a combustion chamber; and (c) an incinerator feed means; the improve­ ment comprising: (d) said boiler means having metal structure defining an elongated secondary combustion chamber, and having a water coolant chamber disposed thereabout; (e) an elongated primary combustion chamber being connected to one end portion of said boiler means and defining flue gas transition means in aligned registry with a secondary combustion chamber, said primary combustion chamber being of a physical dimen­ sion to contain a waste incinerating flame of maximum expected dimension for substantially adiabatic incin­ eration of a predetermined range of waste feeds; (f) said primary combustion chamber having a refractory lining of a character sufficient to with­ stand temperatures above the maximum expected temper­ ature of said waste incinerating flame, said refractory lining also forming a temperature resistant refractory lining for said flue gas transition means; and (g) means for cooling said flue gas transition means and reducing the temperature of flue gas flowing from said secondary combustion chamber to a sufficiently decreased temperature range to minimize corrosion of said carbon steel tube sheets. If an incinerating fuel supply is normally added, an extremely high combustion temperature of perhaps 1,000 to 1,800°C can be achieved for suc­ cessful destruction of toxic substances to obtain an ecologically desirable flue stream. The inciner­ ator structure of this invention accomodates the higher temperature and enlarged flame front while minimizing risk to the refractory and metal heat transfer surfaces. Thus, the addition of a combustion feed flow, the estab­ lishment of a stabilized flame front, and the sus­ taining of relatively high combustion temperatures is effectively accomodated by the incinerator system hereof. The combustion chamber is of a designed dimension correlated with the character of waste material to be incinerated and the fuel necessary to achieve complete combustion of the waste material. The volumetric dimension of the combustion chamber, including its length and width, is determined by the maximum expected volume of the flame in the combustion chamber. The modified combustion chamber or furnace of this invention is particularly constructed so that the horizontal combustion chamber is more elongated and of larger dimension as compared to standard fire tube boilers so that a mix of waste to be combusted (typically a halogenated hydrocarbon gas or liquid) is injected with a feed (natural gas or fuel oil) along with combustion air and steam to establish a stabilized flame front of high temperature within a refractory lined elongate horizontal combustion chamber. Four feeds are provided, one being a sup­ ply of fuel and the second being a flow of atomizing fluid, typically air or steam. A third feed is incor­ porated, namely the liquid and/or gas waste, and the fourth is combustion oxygen and/or air. A flame front is established within the combustion chamber defined within refractory lined cylindrical housing having an out flow passage. At this juncture, the flame front is established of sufficient size and temperature to insure complete conversion of the waste hydrocarbons. The out-flow therefrom has a reasonably regulated temperature and carries combustion products, the waste products being fully consumed and converted to enable the flue gases to be safely discharged. The combustion chamber is secured to the combustion gas entry portion of a standard fire tube boiler with an elongated flue gas receiving passage in aligned registry with the gas flow passage from the combustion chamber. At the end of the flue gas receiving passage the flow path is reversed as it impinges against a tube sheet. The length of the gas flow passzge from the combustion chamber together with the length of the flue gas receiving passage of the boiler permits temperature decrease such that the temperature of the flue gas impinging upon the tube sheet is within an acceptable range for extended service life of the conventional metal tube sheet. Further, the gas flow passage of the combustion chamber is refractory lined and water cooled and extends well into the entrance of the gas receiving passage of the boiler. This feature provides the gas entrance portion of the boiler with efficient protection against elevated temperature during temperature diminishing flow of flue gas into the boiler. The foregoing describes in summary fashion the apparatus which is described in detail hereinafter. An understanding of the description of the preferred embodiments will be aided and assisted by review of the acompanying drawings. The appended drawings illustrate only typical embodiments of this invention and are, therefore, not to be considered limiting of its scope, for the invention may admit to other equally effective embodi­ ments. Figure 1 shows the improved halogenated hydrocarbon incinerator of the present invention in sectional view setting forth details of construction; and Figure 2 is a sectional veiw of an improved halogenated hydrocarbon incinerator representing an aleternate boiler construction embodiment of this invention. Attention is first directed to Figure 1 where the improved incinerator is identified by the numeral 10. The description of the apparatus will begin with that portion of the equipment where the waste is incinerated with atomizing gas, combustion air and fuel, and follows the flow path of the combustion products through the incinerator and out the flue. In very general terms, the numeral 12 identifies a firebox or primary combustion chamber of an elongate generally cylindrical construction, which cylindrical configu­ ration is not intended as limiting, since within the spirit and scope hereof the primary combustion chamber may take other suitable forms. The primary combustion chamber has a remote end wall 14. The wall 14 supports a manifold 16 into which a large flow of combustion air is delivered. The air is forced into the manifold 16 by means of a blower 18. An ample volume of air is delivered to assure complete combustion. The numeral 20 identifies a nozzle assembly which ejects a controlled flow of fuel, waste to be combusted and also an atomizing fluid. The nozzle 20 is physiclly located adjacent the mani­ fold 16 whereby an outflow of combustion air surrounds the plume of atomized vapors coming from the nozzle 20. The nozzle 20 is provided with three feeds. The feed 22 furnishes an atomizing fluid which is either air or steam. It defines an emerging spray extending from the nozzle 20 which supports and carries fuel and waste for combustion. Fuel is delivered through a conduit 26 for the nozzle 20 and is ejected from the nozzle along with the atomizing fluid. A flow a waste (either liquid or gaseous delivered from a suitable waste source through a typical shut off valve) is delivered through a conduit 24. In general terms, the fuel may be fuel oil or natural gas. The waste can be gas or liquid, and typically incorporates a significant volume of halo­ genated hydrocarbons for combusion and disposal. Both the waste and the fuel are delivered to the atomizing fluid flow and all are comingled as they flow at rela­ tively high velocity in an atomized dispersal from the nozzle 20. They are surrounded by a flow of combustion air. By means of a pilot (not shown), the combustion products are ignited and the flame is established within the primary combustion chamber 12. The nozzle assembly and external connective lines are represented somewhat schematically. Typical prepackaged nozzle assemblies can be purchased for the primary combustion chamber 12 (one source is Trane Thermal Company of Pennsylvania, U.S.A). The primary combustion chamber includes the back wall 14 which supports, thereby centering, the nozzle 20 and consequently supports and locates the flame front within the primary combustion chamber 12. The combustion chamber has an elongate cylindrical body 28. It is sized so that the remote end of the flame front is contained within the cylindrical volume defining the primary combustion chamber 12. The physical dimensions of the primary combustion chamber 12 are sized according to the character of waste to be incinerated. Generally, the higher the volume of halogenated hydrocarbons of the waste feed, the larger the primary combustion chamber to ensure adequate dwell time of the waste products in the primary combustion chamber for complete combustion. The primary combus­ tion chamber terminates with outlet conduit or passage 30. Passage 30, being the discharge passage of the primary combustion chamber, is subject to elevated temperature immediately downstream of the flame front. Passage 30 is therefore lined with refractory material 27 which extends in contiguous relation from the refractory lining of the primary combustion chamber 12 to a location well inside the inlet passage or chamber 34 of the fire tube boiler 10. For cooling of the flue gas passing through the passage 30 the refractory lining 27 is surrounded by a cooling chamber 29 through which cooling water flows. The cooling chamber is fed from a water supply or any other suitable supply of coolant medium. While flowing from the primary com­ bustion chamber through the passage 30 the temperature of the flue gas is decreased from the flame temperature range of 1600°C to 1800°C to a temperature level of about 1100°C. Further cooling of the flue gas is achieved in the boiler passages by virtue of the water jacket cooling system thereof. A halogenated waste destruction efficiency of 99.99 percent will result, and an overall combustion efficienty of about 99.9 percent is obtained. This destruction efficiency is advantageously accomplished with less fuel gas as compared with standard boiler systems and with tem­ perature maintenance within the tolerance range of carbon steel. Efficient waste destruction is achieved and more importantly, efficient chlorine recovery, a prime consideration, is effectively achieved. Heat recovery, an ancillary requirement, is also efficiently accomplished. Passage 30 opens into a flared tran­ sition member 32 which then connects with a horizontal flue gas receiving chamber 34. As a matter of scale, the primary combustion chamber 12 and passage 30 can be close in size as in Figure 2 and hence avoid the tran­ sition at 32. The chamber 34 is serially connected downstream from the primary combustion chamber 12 and hence can, in one sense, be called a horizontal or secondary combustion chamber. In that sense, the combustion begins in the combustion chamber 12 and may be substantially complete therein; on the other hand, there may be individual droplets which are ultimately combusted in the secondary combustion chamber 34. The flame front can extend into the transition passage 30 but is is intended to be contained within the primary combustion chamber 12. As will be appreciated, there is a temperature gradient indicative of the fact that most of the combustion occurs within the combustion chamber 12. For this reason, the secondary combustion chamber 34 is less a combustion chamber, but it is aligned with chamber 12 to expand the effective com­ bustion chamber size and capacity to thereby enable the outflow of combustion gases to escape the immediate combustion chamber area, whereby continued use and operation of the device can be obtained without boiler destruction. Some emphasis should be placed on the mater­ ials used in construction of this apparatus. The primary combustion chamber 12 is preferably made of a high quality ceramic refractory material capable of withstanding at least 2,000°C. Ordinarily, the fuel and air flow are such as to maintain temperatures up to about 1,800°C. Depending on the particular nature of the feed, lower temperatures can be sustained while yet achieving full combustion conversion of the waste products. To insure an ecologically safe discharge at the flue, the maximum temperature required for the most difficult combusted product should be the design criteria for material selection. In this light, a combustion chamber construction with materials capable of handling about 2,000°C on a sustained basis is sufficient. The ceramic refractory materials used in this area extend through the water jacketed tube 30 to the transition member 32. That is, from the member 32, alternate and less costly materials can be used because the temperature is substantially reduced and the flue gas is not highly corrosive. Assuming a design criteria of 2,000°C in the primary combustion chamber, the secondary combustion chamber 34 can be designed for a lesser temperature in the range of from 900°C to 1500°C. To this end, it is permissible to use exposed metal surfaces such as special nickel steels. Such alloys can be used to safely resist damage from the temperatures achieved within the chamber 34. Since the device preferably operates at high temperatures to assure substantially complete combustion of the waste, no condensation occurs within the chamber 34. The chamber 34 is thus defined by the surrounding metal wall 36. Typically, this is constructed as a circular member which is concentric relative to the primary combustion chamber 12 and which has a relatively large cross-sectional area. It is supported by a surrounding housing 38. The space around the wall 36 is water filled as explained below. The tubular member 36 extends to and terminates at a return space 40. The return space 40 is defined within a specially shaped member made of refractory materials and identified at 42. The structure 42 has an internal face 44 which is curved and shaped to route the gas flow through a gentle U-turn. The ceramic refractory material 42 is sup­ ported by a surrounding second refractory material 46 which is in turn supported by a metal cap 48. The metal cap 48 is a structural member terminating in a circular flange, having sufficient strength and structural integrity to hold and support the various ceramic members which are affixed to it. By the time gas flow reaches the return space 40, the temperature drops under 1000°C well within the range of efficient serviceability of the carbon steel tube sheets of the boiler. It will be observed that the end of the incinerator can be removed by removing all of the components supported with the member 48. This can typically be achieved by attaching the member 48 to the remainder of the structure with suitable nuts and bolts (not shown). In very general terms, the large gaseous flow at elevated temperature turns through the return space 40 and is deflected by the overhead barrier 50. The gaseous flow is directed toward a set of return tubes 52. There are several return tubes which extend parallel to and above the chamber 34. They open into a flow chamber 54 at the opposite end. In the flow chamber 54, the metal walls 56 and 58 define the flow chamber such that the flowing gases are directed through a U-turn, flowing through return tubes 60. The tubes 60 in turn communicate with another return space 62 and redirect the flowing gases into another set of tubes 64. These tubes open into a manifold 66 and are discharged through a flue 68. As will be observed, the wall 56 defines one end of the structure. It is covered with insulated materials such as refractory material because there is direct gas impingement against this wall. The gas flow at the left hand end is thus directed against the wall 56, accomplishes a full turn, ultimately arriving in the manifold 66 to be discharged through the flue 68. This is similar to the flow pattern established at the right hand end where the gas is directed through two separate 180° turns. As will be observed in common between both ends of the equip­ ment, a metal structure supporting ceramic refractory material directs the gas to turn along the paths as described. Several features of this apparatus should be noted. The right hand end comprises a separable assem­ bly for servicing the equipment. To obtain some inform­ ation on the continued successful operation of the device, a thermocouple 70 is incorporated and a similar thermocouple 72 is likewise included. They measure and indicate the temperatures in different portions of the equipment. If desired, a sight glass 74 is likewise included, being located to view the chamber 34 and the combustion chamber 12. This view through the sight glass coupled with the two thermocouples helps an operator know the condition within the equipment. In like fashion, a similar thermocouple 76 is incorporated at the flue. As will be understood from the materials indicated in the drawing, the structure including the tube sheets and return tubes is primarily fabricated of carbon steel and is not particularly able to resist excessive heat and corrosion damage. The several tubes 52, 60 and 64 are parallel to one another and are supported by tube sheets. At the right hand end, a tube sheet 78 supports the tubes in parallel alignment with one another. In like fashion, a similar tube sheet 80 at the left hand end supports the tubes so that they are arranged in parallel ranks. There are several return tubes 52 having an aggregate cross­ -sectional area to suitably conduct the gas flow emerging from the primary combustion chamber 12. No constriction arises because the number of tubes 52 is selected to insure that the back pressure is held to a minimum. In like fashion, the tubes 60 and 64 are likewise replicated to assure an adequate gas flow route. The several return tubes supported by the tube sheets cooperate with a top wall 82 and outlet 84 to define a steam chest. Specifically, water is introduced and fills the steam chest. Water is added and steam is recovered through the port 84. The water is maintained to a depth of at least three inches over the top tubes. Steam is delivered through the port 84 at a suitable pressure and temperature for use else­ where. Accordingly, water fills the chamber or cavity fully surrounding the wall 36 defining the secondary combination chamber 34 and rising to a height as described and fully enclosing the secondary combustion chamber 34 and the return tubes 52, 60 and 64. A suitable water supply control system (not shown) delivers a sufficient flow of water whereby steam is discharged and can be used for utility recovery. The water is heated by heat transferred through the chamber 36 and all the tubes above it. The steam in the sur­ rounding steam chest stabilizers the metal parts tem­ perature. The flue gas discharged from the apparatus has a temperature of perhaps 15°C to 50°C higher than the steam temperature. It is discharged at the outlet 68, and is preferably delivered to a device which scrubs the flue gas to remove vaporous hydrochloric acid. Referring now to Figure 2 of the drawings, a fire tube boiler is illustrated generally at 90 having an external boiler shell 92 which is formed of conven­ tional, low cost material such as carbon steel provided with an exterior installation. The boiler 90 forms a secondary combustion chamber 94 having a carbon steel lining 96 surrounded by a water jacket 98. The boiler structure defines a front tube sheet 100 and a com­ bustion chamber tube sheet 102 which provide structural support for a plurality of parallel second pass tube members 104. These tube members are composed of standard low cost material such as carbon steel and function to conduct the flow of flue gas from the secondary combustion chamber 94 through a boiler water chamber 106. Water in the boiler chamber is maintained at a level above the tube members. A plurality of third pass tube members 108 ae supported at one end by tube sheet 100 and at the opposite end by a rear tube sheet 110. The boiler tubes 104 and 108 communicate with a flue chamber 112 formed by a flue chamber wall structure 114 connected to the tube sheets 100. Within the flue chamber 112 flow from the second pass tube members 104 reverses direction and enters third pass tube members 108. Exiting flue gas from the third pass tube members 108 enters a gas outlet passage 116 defined by a rear flue chamber housing 118 connected to the rear tube sheet 110. Combustion product gases at the out­ let passage 116 will be in the range of from 15°C to 35°C above saturated steam temperature. This tem­ perature is measured by a temperature sensor 120. The boiler water chamber 106 is provided with a steam outlet 122 which is in communication with a steam chamber 124 at the upper portion of the boiler. At the rear end of the boiler a refractory plug 126 is provided to close a manway opening of the combustion chamber. This refractory plug includes a site glass 128 for visual inspection of the com­ bustion chamber and a temperature sensor 130 for detection of flue gas temperature in the secondary combustion chamber. The fire tube boiler 90 is of a fairly conventional nature and being composed of low cost material such as carbon steel, it will not typically withstand significantly elevated temperatures such as are present during combustion of highly halogenated hydrocarbon waste materials and it will not with­ stand excessive corrosion which typically occurs when carbon steel materials are in contact with flue gas at significantly elevated temperatures. Accordingly, the boiler system 90 is modified to provide an elongated burner or primary combustion chamber, illustrated generally at 132, which extends forwardly of the front tube sheet 100 of the boiler. The primary combustion chamber 132 is defined by a housing structure 134 which is lined with a high temperature refractory material 136 which is capable of withstanding flame front temperature in the order of 2000°C. The refractory lining is designed to minimize heat losses thus allow­ ing combustion to approach adiabatic conditions to allow combustion of waste material having low fuel value feed with minimum support fuel. The initial portion of the primary combustion chamber 132 is formed by a fire brick material having high alumina contact. This fire brick material is surrounded by an insulating refractory material which provides an acid resistant membrane. The exterior housing 134 is also insulated and provides a wind/rain shield to insulate the burner mechanism from the effects of weather. At the connection of the primary combustion chamber 132 with the front tube sheet 100 the refrac­ tory lining extends past the front tube sheet well into the secondary combustion chamber 94 thus protecting carbon steel metal surfaces from corrosion by high temperature flue gas which may be in the order of 1100°C to 1550°C at the inlet throat of the fire tube boiler. A water jacket 138 is secured to the front tube sheet and defines a coolant chamber or "wet throat" which is in communication with boiler chamber 106 via openings 140. This wet throat boiler furnished extension maintains the carbon steel at the desired temperature in the transition of flue gas from the refractory lined combustion chamber to the water walled boiler furnace. At the front end of the primary combustion chamber mechanism 132 is provided an air nozzle 142 (such as may be composed of Hastelloy-C or Inconel). To the burner air nozzle 142 is connected a combustion air baffle 144 and a plurality of combustion air swirl vanes 146. A liquid and gas feed injection nozzle is supportive by the air swirl vanes and includes an appropriate tip for air atomization. A Hastelloy-C tip may be provided for atomizing the liquid and gas feed with air and a tantalum tip may be provided for steam atomization. The nozzle is provided with a feed line150 for an atomizing fluid (steam or air) and a feed line 152 for combustable process or fuel gas. A supply line 154 is provided for RCl and HC (chlori­ nated waste mixed with various hydrocarbons) and a supply line 156 is provided for fuel oil. Another line 158 is provided for supply of combustion air to the system which is appropriately mixed by combustion air swirl vanes with the waste RCl and fuel feeds. Another fuel supply line 160 (mixed with air) is provided in the event inert waste gas contaminated with RCl must be boosted in temperature. The temperature of the flame front in the combustion chamber 132 is monitored by means of a temperature sensor 162. From the foregoing it is apparent that the present invention provides an enhanced device and method for the combustion of chlorinated hydrocarbons for the recovery of the chlorine as muriatic acid with energy recovery as steam. Refitting a packaged fire tube boiler that has been modified and operated at conditions to prevent failure from corrosion from a burner of a special design to accomplish waste combus­ tion with a minimum loss of heat within a minimum volume can reduce support fuel requirements in the range of from 25 percent to 50 percent. Reduction of support fuel requirements can significantly increase the HCl concentration in the combustion product gases which enhance the recovery of HCl. Also, reducing support fuel requirements can significantly reduce the size of the equipment and the operating costs because air requirements can be reduced accordingly. In accordance wth the foregoing, it is evident that standard or conventional direct-fired packaged fire tube boilers modified to burn chlorinated hydrocarbons (RCl and HC) can successfully burn certain chlorinated hydrocarbons having physical and/or chemical properties that require a longer residence time than that provided by standard fire tube boiler design. Refitting the modified boiler with a burner of special design for the specific requirements (turbulance, residence time and temperature) of a particular chlorinated hydrocarbon feed waste, off-spec products, by-products, and spent solvents) can accomplish product and energy recovery to a greater extent than was previously possible. The burner design of standard or conventional direct-fire package fire tube boilers can be modified according to the present invention to burn chlorinated hydrocarbons and thus provide only limited alternatives for introducing in multiple liquid and gaseous chlor­ inated hydrocarbon feeds of various properties and fuel quality. Refitting the boiler device with a burner of special design, allows the injection of essentially inert gases contaminated with small amounts of RCls and HC, separate and apart from the support fuel and fuel quality RCl feeds, for efficient destruction of these hazardous contaminants while maintaining safe and reliable combustion control. The use of a boiler device for the recovery of energy in the form of steam from the combustion of RCls also serves to quench the hot combustion gases for HCl recovery in downstream absorber equipment. The use of a boiler for cooling the combustion gases, instead of an evaporated quench system of conventional RCl burner design, enhances the recovery of HCls as a more concen­ trated muriatic acid product, since there is only water vapor from combustion air and as a product of combustion to contend with in the HCl absorber design. A particularly important advantage of the present invention is the possibility of introducing completely inert gas into the flame for combustion and conversion. Cost of operation is thus reduced as the volumetric flow is reduced (even when disposing of inert gas) whereby steam recovery supplied part of the cost of operation. If desired, hydrochloric acid recovery from the flue gas discharge by suitable con­ nected downstream equipment enables more economic recovery of the discharged flue gas.

Claims: 1. In a waer-cooled, horizontal fire tube boiler having; (a) a boiler section having a generally closed shell having a vertically disposed metal tube sheet at each end, said shell holding water between said ends, a combustion chamber extending along the length thereof, and within, said shell, and communi­ cating through said tube sheets, a plurality of relatively small metal return-tubes extending the length of, and within the boiler shell and communi­ cating through said tube sheets, the combustion chamber and the return-tubes being in spaced hori­ zontal relationship, and said boiler section defines a folded multi-segment flue gas discharge path there­ through; (b) two end section means, at least one of which is affixed; (c) said shell and said end section means having surfaces, except for the tube sheet surfaces, which are exposed to the combustion gases when the boiler is in operation, made of corrosion resistant material or covered with an amount of insulation pre­ determined to maintain the temperature of such sur­ faces within a predetermined temperature range during operation; (d) a front end nozzle section adjacent to the combustion chamber; (e) a means for supplying water into said shell; (f) a means for removing steam from said shell; and (g) flue means for removing combustion gases from one of the end sections; the improvement comprises: (h) two combustion chambers wherein (i) the primary combustion chamber has a front end nozzle section adjacent to the confined primary combustion chamber for containing combustion gases; (ii) said primary combustion chamber commun­ icating with a secondary combustion chamber and into said return-tubes; (iii) said front end nozzle section having feed means for feeding air, supplemental fuel, and halo­ genated hydrocarbons into a burner nozzle, within the primary combustion chamber; (iv) means for blowing air past said nozzle to define a flame front having a temperature in the range from 1,000 to 1,800°C to combust halogenated hydrocarbons; (v) said primary combustion chamber having an elongate extent sufficient to enclose therein the flame front, and wherein said primary combustion chamber termminates opposite said burner nozzle in an aligned and streamlined relation therewith, insulation covered wall means defining an outlet directing flue gas flow from said primary combustion chamber into said secon­ dary combustion chamber; (vi) said secondary combustion chamber is relatively long and extending along the length of, and within, said shell, and communicating through the tube sheets; (vii) the outlet directing the gas flow being sufficiently spaced from the flame front and sufficiently long that flue gas temperature at the end of said sceondary combustion chamber is less than 1,000°C at entry into the folded multi-segment flue gas discharge path; and (viii) an end section means having a confined space for containing combustion gases, said space com­ municating with said secondary combustion chamber and said return-tubes and defining a portion of said folded multi-segment flue gas discharge path. 2. The apparatus of Claim 1 wherein said primary combustion chamber includes an elongate cylindrical side wall opening into said chamber, and including auxiliary waste injector nozzle means into said primary combustion chamber located on said side wall. 3. The apparatus of Claim 1 wherein said secondary combustion chamber comprises an elongate circular structure internally lined with refractory material, and which has a lengthwise extent in con­ junction with said primary combustion chamber to define a region of elevated temperature sufficiently long to obtain a dwell time over a specified minimum whereupon the waste halogenated hydrocarbons are oxidized before turning into said multi-segment flue gas discharge path. 4. The apparatus of Claim 3 wherein said primary combustion chamber includes a circular end portion supporting said nozzle, said nozzle location determining alignment of the fire front in said primary combustion chamber and said secondary com­ bustion chamber, and wherein said nozzle, in conjunction with a specified gas flow therealong, forms a flame front discharging waste flue gas at less than 1000°C into a first U-turn in the multi-segmented flue gas flow path. 5. The apparatus of Claim 4 including a nickel alloy metal member defining said secondary com­ bustion chamber, and wherein said secondary combustion chamber is encircled by water on the exterior thereof and within said shell. 6 The apparatus of Claim 4 including first and second serially arranged sets of return tubes in sufficient total cross-sectional area to flow flue gas to said flue means. 7. The apparatus of Claim 4 including transition means connected between said primary com­ bustion chamber and said secondary combustion chamber, said transition means tapering between two circular ends, and being formed of refractory material. 8. The apparatus of Claim 4 wherein said primary combustion chamber includes a surrounding cyclindrical wall supporting auxiliary nozzle means for injecting a flow of inert halogenated hydrocarbon waste into the flow from said nozzle for combustion before emerging from the flame front. 9. The apparatus of Claim 8 including means for delivery of atomizing fluid with said halo­ genated hydrocarbon waste. 10. In a water-cooled horizontal fire tube boiler for incineration of waste materials which con­ tain highly chlorinated hydrocarbons, having: (a) boiler means having a water coolant chamber and carbon steel tube sheets supporting a plurality of water cooled gas flow tubes; (b) a combustion chamber; and (c) an incinerator feed means; the improvement comprises: (d) said boiler means having metal structure defining an elongated secondary combustion chamber, and having a water coolant chamber disposed therebout; (e) an elongated primary combustion chamber being connected to one end portion of said boiler means and defining flue gas transition means in aligned registry with a secondary combustion chamber, said primary combustion chamber being of a physical dimen­ sion to contain a waste incinerating flame of maximum expected dimension for substantially adiabatic incin­ eration of a predetermined range of waste feeds; (f) said primary combustion chamber having a refractory lining of a character sufficient to with­ stand temperatures above the maximum expected temper­ ature of said waste incinerating flame, said refractory lining also forming a temperature resistant refractory lining for said flue gas transition means; and (g) means for cooling said flue gas transition means and reducing the temperature of flue gas flowing from said secondary combustion chamber to a suffi­ ciently decreased temperature range to minimize cor­ rosion of said carbon steel tube sheets. 11. Apparatus as recited in Claim 10, wherein said flue gas transition means is of reduced cross-sectional dimension as compared to the cross­ -sectional dimension of said primary combustion chamber thereby forming a restriction between said primary combustion chamber and said secondary combustion chamber of said boiler. 12. Apparatus as recited in Claim 11, wherein a water jacket is disposed about said flue gas transition means and forms a transition coolant chamber for said flue gas transition means, said coolant chamber being in communication with said water coolant chamber. 13. Apparatus as recited in Claim 10, wherein said flue gas transition means is of sub­ stantially the same cross-sectional dimension as the cross-sectional dimension of said secondary combustion chamber of said boiler. 14. Apparatus as recited in Claim 13, wherein a water jacket is disposed about said flue gas transi­ tion means and forms a transition coolant chamber for said flue gas transition means, said transition coolant chamber being in communication with said water coolant chamber. 15. Apparatus as recited in Claim 10, wherein said primary combustion chamber includes feed means for selectively feeding waste material, air, fuel and steam as needed to maintain an inciner­ ation flame in said primary combustion chamber in the range of from 1000°C to 1800°C for combustion of halo­ genated hydrocarbons. 16. Apparatus as recited in Claim 10, wherein said primary combustion chamber is of generally cylindrical configuration and is sufficiently elongate to confine therein a significantly large incineration flame to achieve substantially complete combustion of a feed including halogenated hydrocarbons.

Inventors: BUICE, JACK E.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1986
Main classification: F23G7
IPC codes: F22B7, F23G7, F23G5