Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
  • F23C3/00—Combustion apparatus characterised by the shape of the combustion chamber
  • F23C3/006—Combustion apparatus characterised by the shape of the combustion chamber the chamber being arranged for cyclonic combustion
  • F23C3/008—Combustion apparatus characterised by the shape of the combustion chamber the chamber being arranged for cyclonic combustion for pulverulent fuel
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
  • F23C6/00—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion
  • F23C6/04—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection
  • F23C6/045—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection with staged combustion in a single enclosure
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
  • F23C7/00—Combustion apparatus characterised by arrangements for air supply
  • F23C7/02—Disposition of air supply not passing through burner
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J1/00—Removing ash, clinker, or slag from combustion chambers
  • F23J1/08—Liquid slag removal

Definitions

• This invention relates generally to fuel co - bustors, and, more particularly, to a slagging combustor in which the fuel is pulverized coal.
• the fuel is pulverized coal.
• non-combustible ash and mineral components cannot be allowed to accumulate within the combustion chamber, or serious operational problems will be experienced.
• the temperature in the chamber is maintained high enough to allow the slag to be removed in liquid form by the action of shear forces and/or gravitational forces acting on the slag.
• This slagging capability will also have benefits related to operation of downstream equipment interacting with the product flowstream.
• a slagging combustor may have different re ⁇ quirements, such as overall stoichiometry, imposed on it by the characteristics of a downstream process utilizing the products of combustion.
• an ideal slagging combustor should have good slag recovery characteristics and should operate at a relatively low temperature, to minimize heat losses and maximize efficiency.
• the degree of combustion of the coal in a slagging combustor will depend in part on the intended application of the gaseous products of combustion. For example, if the combustor is to be employed to produce gas for use as a fuel in a conventional power generation plant, or in chemical processes, the gases exiting from the combustion chamber should still be relatively rich in combustibles. Accord ⁇ ingly, if a coal combustor is to be used as such a gas generator, the combustion process should take place in a relatively fuel-rich environment. In terms of stoichio- metry, a stoichiometric ratio as low as 0.3 might be desirable for subsequent combustion in a boiler or use as feed stock in a chemical process.
• the gas were to be immediately employed in a combustion or heat exchange process, it might be desirable to provide a gas at a higher temperature, but with a lower equivalent heat value in the combustibles in the gas. This could be done by more completely combusting the coal in the slagging combustor, i.e. at a higher stoichiometric ratio.
• the desired stoi- chiometry of a slagging combustor would be substantially different if the output gases were to be used in a ag- netohydrodynamic (MHD) electric power generator.
• An MHD generator utilizes a high-temperature, high-velocity plas a which is passed through a magnetic field to generate electricity directly, without the use of rotating machinery.
• the gaseous products from the slagging combustion stage may be lower in combustibles content and higher in temperature and heat content.
• the products of combustion may then be subject to further combustion after leaving the slagging combustor.
• Addi ⁇ tional oxidizer, and sometimes additional fuel, may be added to the exiting gases for this purpose.
• the slagging combustor should still ideally provide good slag recovery and relatively low operating tempera ⁇ tures.
• the desired stoichiometry of the combustion process will depend on the requirements of the downstream application. Acceptable combustor operation and combustion product properties will also be dependent on the temperature and composition of the oxidizer gas, and the type and size of the coal particles. Selection of the appropriate para ⁇ meters, to satisfy the requirements of the downstream application, typically involves a number of practical design trade-offs. For example, preheating the oxidi- zer gas to a higher temperature and thereby permitting reactions at a lower stoichiometric ratio might still meet the requirements of the downstream application, but would obviously require either the consumption of more energy in the preheating stage or the addition of a heat exchanger. The first of these alternatives may or may not comport with the overall energy requirements of the appli- cation, and the second may not even be feasible.
• the stoi ⁇ chiometric ratio in a slagging combustor is of critical importance to the rate of slag recovery. If the ratio is too low, temperatures will also tend to be low, and the slag may not liquify sufficiently to facilitate recovery. Conversely, if the ratio is too high, the temperature may be so high that a significant proportion of the slag is lost by vaporization. In theory at least, the effective slagging range has been thought to lie above 0.4 and up to 1.0 for the combustor as a whole. However, the stoichiometry desired to meet the requirements of the downstream appli ⁇ cation may not fall within this theoretical slagging range. For example, if the combustor is to act as a gas generator, a stoichiometric ratio as low as 0.3 might be preferred.
• a coal combustor of this general type should ideally be capable of matching the overall combustor stoichiometry, and other characteristics of the slagging combustor, with the requirements of the downstream application of the com ⁇ bustor.
• the slagging combustor should provide a high rate of slag recovery, a relatively low heat loss, and therefore a relatively high thermal efficiency.
• prior art combustors it has not been possible to satisfy all of these objectives simultaneously. For example, good slag recovery, in conventional combustors, is not consistent with a relatively low temperature and low stoichiometric ratio.
• the present invention resides in a slagging coal combustor, having a head end and an exit end, in which oxidizer is introduced in such a manner that at least a portion of it flows away from the exit end and toward the head end, coal being introduced into the oxidizer flowing toward the head end, to provide an initial phase of combus ⁇ tion in the head end.
• Combustion in this first phase can take place at a stoichiometric ratio much less than that of the combustor as a whole.
• the invention has application as well to combustors of other fuels.
• the essential elements of the invention in its broadest sense are means for introducing oxidizer in such a manner that a portion of it flows toward the head end, and means for injecting fuel into this oxidizer portion to provide the first phase of combustion in the head end.
• the means for injecting oxidizer gas and pulverized coal are so configured that at least a portion of the oxidizer gas stream flows toward the head end of the chamber and is there reacted with the coal fuel in the first phase of combustion.
• gases from the first phase of combustion are further combusted with the remaining portion of the oxidizer gas, which flows toward the exit end of the chamber.
• the stoichiometric ratio in the first phase of combustion in the head end which is approximately one half of the overall ratio for the combustor, may, for example, be as low as 0.3 for some designs. Contrary to generally accepted practice with respect to effective slag removal, extre e- ly good slag removal characteristics can be obtained in this low stoichiometric range.
• the combustor of the invention When used for supplying high-temperature gases to an MHD generator, the combustor of the invention operates at an overall stoichoimetric ratio selected to provide the best combination of slag recovery characteristics in the head end and exit gas conditions matching the requirements of the MHD generator. In a presently preferred embodiment, an overall ratio of approximately 0.6 is used, with a ratio of ap- proximately 0.3 in the head end.
• the oxidizer gas when introduced tangentially into the combustion chamber, splits into two streams.
• One stream has an axial velocity component directed toward the exit end of the chamber while the other portion has an axial velocity component directed toward the head end, into which the fuel is injected.
• the two streams are approximately equal in volumetric flow rates. Because the fuel is initially combusted with a relatively low volume of oxidizer, first- phase combustion at the head end of the chamber takes place at a relatively low stoichiometric ratio. There is a correspondingly low reaction temperature and a relatively high efficiency, because of the reduced heat loss at the lower temperature. However, highly effective slag removal is obtained in these conditions.
• the slagging stage is more efficient thermodynamically, and provides excellent slag recovery. Unburned gases from the first combustion phase then react with the remaining or exit-end stream of the oxidizer gas, and this second phase of combustion takes place at a higher stoichiometric ratio.
• the overall ratio can be approximately 0.6 to 0.9, with a corresponding head-end ratio of 0.3 to 0.45. Because of a relatively high t ⁇ m- perature in the exit end, it may be made relatively shorter in length than is possible in a conventional combustor of the same type. This reduces the heat loss from the chamber and improves the overall thermodynamic efficiency of the combustor.
• the combustor may be operated at a relatively low overall stoi ⁇ chiometric ratio by diverting all of the oxidizer gas toward the head end of the chamber, and regulating the flow rate of the oxidizer to provide the desired ratio. In this case, effective slag removal is still provided in the head end of the chamber, but since no oxidizer is allowed to flow directly toward the exit end, there is no second phase of combustion to provide a higher overall stoichiometric ratio. Consequently, the overall ratio for the entire combustor in this embodiment is the same as the localized ratio for the head-end combustion phase.
• Coal injection into the first-phase combus ⁇ tion zone can be effected by a pintle nozzle disposed axially in the head end and directing fuel flow into that portion of the oxidizer gas flowing toward the head end.
• fuel can be injected through fuel inlets disposed peripherally around the chamber, to direct the flow into the head-end portion of the oxidizer gas flow.
• the means for removing slag from the chamber includes a slag port disposed at the bottom portion of the cylindrical wall of the chamber.
• the head end of the chamber is the lowermost end and the exit is the uppermost.
• the slag port is located at the head-end.
• the invention in its broadest terms comprises the steps of injecting oxidizer gas peripherally into a chamber having a head end and an exit end, in such a manner that at least a portion of the flow is directed towards the head end, injecting fuel, such as pulverized coal, into the head end in such a manner that combustion takes place initially at a relatively low stoi- chiometric ratio and low temperature, regardless of the end use of the gaseous products of combustion and regardless of the overall stoichiometry of the combustor, removing any non-combustible slag from the chamber, and allowing the essentially gaseous products of combustion to exit the chamber.
• fuel such as pulverized coal
• the steps of injecting oxidizer gas and injecting pulverized coal include injecting the oxidizer gas tangentially into the chamber at a point between the head end and the exit end of the chamber such that the . oxidizer gas flow splits into two approximately equal portions having opposite axial components, and in ⁇ jecting the pulverized coal into the oxidizer gas portion flowing toward the head end, wherein a first phase of combustion occurs in the head end at a stoichiometric ratio of approximately one half of the overall stoichiometric ratio for the combustor.
• substantially all of the oxidizer gas flow is directed toward the head end in such a manner that the head-end stoichiometric ratio remains substantially the same as in the embodiment not used as a gas generator.
• the present invention represents a significant advance in the field of coal combustion and gasification.
• a novel coal combustor achieves good slag removal rates while attaining high thermodynamic efficiency, low heat loss and complete burning of carbon.
• the combustor of the invention allows for convenient matching of its thermo ⁇ dynamic characteristics with those of a desired downstream process.
• FIGURE 1 is a simplified perspective view of a coal combustor embodying the present invention, including the slagging combustor and slag removal apparatus, and also showing an exit combustion stage which is not part of the invention.
• FIG . 3 is a fr agment ary sectional vi ew o f a pintle nozzle used to inj ect coal and , for MHD and other selected applications, an additive material, into the combustor;
• FIG. 4 is a diagrammatic view showing typical flow patterns of fuel, oxidizer gas and combustion products within the slagging combustor;
• FIG. 5 is a diagrammatic elevational view showing the configuration of a first embodiment of the invention, having a tangential oxidizer inlet and a volute exit port;
• FIG. 5a is an end view of the embodiment shown in
• FIG. 6 is a diagrammatic elevational view showing a second embodiment of the invention, having a tangential oxidizer inlet, a symmetric exit port and a shortened exit end portion;
• FIG. 6a is an end view of the embodiment shown in FIG. 6, taken in the direction of the arrow 6a in FIG. 6;
• FIG. 7 is a diagrammatic elevational view of a third embodiment of the invention similar to the second embodiment shown in FIG. 6 but having the slag tap located in the head end rather than the exit end;
• FIG. 7a is an end view of the embodiment shown in FIG. 1 , taken in the direction of the arrow 7a in FIG.7;
• FIG. 8 is a diagrammatic elevational view showing a fourth embodiment of the invention having a recessed volute oxidizer inlet, a symmetric exit port and a head-end slag tap;
• FIG. 8a is an end view of the embodiment shown in
• FIG. 8 taken in the direction of the arrow 8a in FIG. 8;
• FIG. 9 is a diagrammatic elevational view of a fifth embodiment of the invention having two slagging combustors, each with a recessed volute oxidizer inlet, and a head end with a fuel injector and a slag tap, the two combustors being matched to a common, centrally located exit port;
• FIG. 10 is diagrammatic elevational view showing a sixth embodiment of the invention with a vertically oriented combustion chamber, a recessed volute oxidizer inlet, a symmetric exit port, peripheral coal injectors, and a head-end slag tap;
• FIG. 10a is a plan view of the embodiment shown in FIG. 10;
• FIG. 10b is a sectional view of the embodi ⁇ ment shown in FIG. 10, taken substantially along line lOb-lOb in FIG. 10;
• FIG. 11 is a diagrammatic elevational view of a seventh embodiment of the invention having a vertically oriented combustion chamber similar to that shown in FIG. 10, but including an inlet flow diverter to divert all of the inlet oxidizer flow to the head end of the chamber; and
• FIG. 11a is a sectional view of the embodiment shown in FIG. 11, taken substantially along line lla-lla in FIG. 11.
• the present invention is principally concerned with a pulverized coal combustor, and more particularly with a slagging coal combustor.
• slagging coal combustors the non-combustible ash and mineral components of the coal are removed in liquid form, so that these constituents do not remain in the gases produced by the combustor.
• a coal combustor should be adaptable to provide gas to an MHD generator, or to provide fuel gas for subsequent burning in boilers or in other chemical processes, and still should maintain a high rate of slag recovery and a high thermal efficiency.
• Prior coal combustors have traditionally employed an oxidizer flow pattern having an axial component directed towards the exit end, and have not been able to achieve the desired combination of ideal characteristics.
• a coal combustor is provided with fuel and oxidizer injection means which cooperate in such a manner that combustion takes place initially in the head end of the combustor at a relatively low stoichiometric ratio, regardless of the end use of the gaseous products of combustion and regardless of the overall stoichiometry of the combustor.
• Extremely good slag recovery is provided at the relatively low local stoichiometric ratio in the head end, and heat losses are minimized, with a corresponding maximization of efficiency.
• a second combustion phase may optionally be provided to yield a higher overall stoichiometric ratio, for use in conjunction with an MHD generator, for example. If the second combustion phase is omitted, a relatively low overall stoichiometric ratio is then provided, such as when the combustor is operating as a synthesis gas generator.
• the apparatus of the invention includes a slagging coal combustor, indicated generally by reference numeral 10, and having a tangential oxidizer inlet 12 and an axial coal inlet 14.
• the combustor 10 comprises a generally cylindrical reaction chamber 16, shown as being disposed with its longitudinal axis horizontal, the cylinder having an exit end 18 through which the products of combus ⁇ tion leave the chamber, and a head end 20 into which the pulverized coal fuel is introduced.
• the exit end 18 includes an exit assembly 22 usually referred to as the symmetrical type.
• a symmetrical exit is one in which the exit path followed by the products of combustion is symmetrical with respect to the axis of the combustor, i.e. the exit path extends from the center of the
• FIG. 1 also includes a further exit combustion stage 24 into which further oxidizer and/or fuel may be introduced, through the inlet 26.
• This exit stage 24 is illustrative of a typical environment for the combustor, but is not essential to the present invention, since the slagging combustor will operate equally well without the exit stage.
• unburned minerals or ash are removed as liquid slag from the chamber 16, through a slag port located low on the cylindrical wall of the chamber close to the exit end 18.
• the port is connected to a slag removal assembly 28, the details of which are not critical to the present invention.
• the entire chamber 16 and the oxidizer inlet 12 are cooled by a fluid, such as water, passed through coolant inlets 30 on top of the cylinder and emerging from coolant exits at the bottom, some of which are shown at 32. Cooling of the combustion chamber 16 produces a solidified layer of slag on the chamber walls.
• the solid layer of slag protects the chamber walls from erosion by liquid slag and by burning fuel particles, and also provides a relatively low conduc ⁇ tivity insulating layer to reduce heat losses from the chamber.
• the walls have a large number of upstanding pins affixed to them, as shown at 34 in FIG. 5.
• the pins 34 are approxi ⁇ mately 1/8 inch (3.2 mm) in diameter and 1/4 inch (6.4 mm) long, welded to the chamber walls at approximately 3/4 inch (19.2 mm) spacing.
• the exit combustion stage 24 is used only in the event that it* is required for matching the
• FIG. 2 shows in diagrammatic form the basic configuration of the slagging combustor.
• Oxidizer gas is introduced tangentially into the combustion chamber 16 through a rectangular port located between the head end 20 and the exit end 18.
• Fuel from the coal inlet 14 is dis ⁇ persed along a generally conical spray having a substantial radial velocity component.
• a half angle of approximately 60 with respect to the central axis of the cylinder 16 is used.
• air from the oxidizer inlet 12 diverges into two separate paths, with respect to the axial component of flow of the oxidizer.
• That portion of the oxidizer flowing back towards the head end 20 will encounter fuel from the coal inlet 14, and combustion will take place in the head end at a stoichoimetric ratio of approximately half the overall ratio for the entire com ⁇ bustor. Fuel particles leaving the nozzle 14 will be substantially heated as they traverse the head end to meet the oxidizer gas near the chamber walls. Thus, if the overall stoichiometric ratio is 0.58, as in an MHD generator application, the stoichiometric ratio in the first combus ⁇ tion phase in the head end will be approximately 0.29. For this MHD application, additional oxidizer is added in the inlet to the MHD generator (not shown) .
• This rotational or cyclonic flow is important in that it provides a relatively long path over which burning of the fuel particles can take place and slag can be formed.
• the swirling action enhances fuel and oxidizer mixing, and directs entrained material outward to the wall surfaces.
• An annular baffle 40 prevents, for all practical purposes, any flow of slag beyond the exit end 18 of the slagging combustor.
• Liquified slag principally from the head end 20, flows towards the slag tap 28 under the effects of gravitational force and shear force between the slag and the adjacent moving combustion gases.
• an additive material may be injected axially with the coal fuel, as indicated at 41 in FIG. 2, to increase the electrical conductivity of the resultant exiting gases or to otherwise modify the exhaust gas species.
• Flow of the additive material has no signifi ⁇ cance in the present invention, however, except to the extent that it may be injected with sufficient velocity to avoid being captured in outflowing slag and to react with the hot exhaust gases.
• FIG. 3 shows in sectional form a typical pintle nozzle structure.
• the pintle 14 is cylindrical in shape and has a number of annular elements defining an axial passage 42 for the additive material, two concentric annular pass ⁇ ages 43 and 44 joined in fluid communication at the end of the pintle, as shown at 45, to provide a cooling fluid path, and a surrounding annular fuel passage 46.
• the annular fuel passage 46 terminates in conical exit port 48 extending in a continuous circle around the periphery of the pintle. Coal is ejected in a conical sheet from the exit port 48.
• An additional annular cooling passage 49 is provided between the fuel passage 46 and the outside surface of the pintle.
• FIGS. 5-11 the invention may be used in a variety of embodiments, depending on the needs of the associated downstream application.
• FIG. 5 there is shown a basic configuration utilizing the principles of the invention. Included are the coal pintle nozzle for injection of coal at 14, a tangential inlet 12, slag tap 28, and an exit shown at 22a.
• the coal could be alternatively injected by means of peripheral fuel inlet ports, such as those shown at 60 in FIGS. 10 and 11.
• the exit 22a is a volute exit shown in more detail in FIG. 5a.
• the radius of the exit assembly increases from a minimum value to a maximum value, and an exit duct merges tangen- tially with the assembly at its point of maximum radius.
• This is to be distinguished from the symmetrical exit (FIG. 6a) , wherein an exit duct merges with a cylindrical exit assembly symmetrically, i.e., along a radius.
• the object is to provide a uniform, non-swirling flow in the exit duct.
• FIGS. 6 amd 6a differs from that of FIG. 5 in two respects.
• a simpler symmetrical exit 22b is shown.
• the exit 22b is located much closer to the inlet, i.e., the overall length of the slagging stage is reduced. This reduction is made possible because the second phase of combustion, in the exit end 18 of the chamber 16, takes a relatively short time, since it involves only gaseous components at a high temperature, the solid fuel having been practically completely combusted in the head end.
• the more compact design of the FIG. 6 embodiment results in a further reduced heat loss and increased efficiency, while still maintaining good slag recovery.
• FIGS. 7 and 7a The embodiment shown in FIGS. 7 and 7a is similar to that shown in FIG. 6, except that the exit end combus- tion phase takes place in an even smaller volume, since the oxidizer inlet, referred to as 12c, is moved much closer to the exit end 18 of the chamber 16, as a consequence of locating -the slag tap 28c at the head end.
• the coal in ⁇ jector has been accordingly lengthened and effectively moved toward the exit end with the inlet 12c.
• the head end volume is correspondingly increased by relocation of the slag tap, and, as in all of the embodiments shown, most of the slag removal function is taking place in the first phase of combustion, at the head end.
• the tangential oxidizer gas inlet has been replaced by a volute inlet 12d, usually referred to as the recessed volute type.
• the same volume of oxidizer gas can be introduced through the volute inlet as through
• the recessed volute 12d shown in more detail in FIG. 8a, introduces the oxidizer gas in a more symmetrical fashion about the walls of the chamber 16.
• the oxidizer circulating in the volute spills over the volute edges in a
• volute inlet introduces oxidizer flow uniformly about the periphery of the chamber, rather than
• FIG. 9 there is a double-ended slagging combustor, in which two head ends 20 and 20' are disposed one on each side of a central exit region 50, there being two inlets 12e of the recessed volute type shown in the FIG. 8 configuration. There are also two slag taps 28e and two coal injectors 14 and 14'.
• the principal advantage of the configuration shown in FIG. 9 is further reduced heat loss, since the exit ends of the FIG. 8 configurations are eliminated.
• there is substantial heat loss from the exit end 22a but in the FIG. 9 con iguration such losses are minimized by joining the exit ends at the central region 50.
• FIG. 10 shows a vertically oriented combustion chamber 16 having a recessed volute inlet 12f, a symmetrical outlet 22f, coal injectors 60 disposed peripherally about the chamber 16 at a location slightly towards the head end 20f from the inlet 12f, and a slag tap 28f located in an axial orientation in the head end.
• the principle of opera- tion is the same as that of the basic configurations already described.
• Coal is injected into the portion of the inlet flow proceeding towards the head end 20f of the chamber 16, and a first phase of combustion occurs at the head end at a relatively low stoichiometric ratio.
• a second stage of combustion can then occur in the exit end of the combustor before the products of combustion exit through the symme ⁇ trical exit 22f.
• any of the aforedescribed embodiments may be modified for operation as gas generators by including means for diverting the entire oxidizer gas flow towards the head end 20 of the combustor.
• the vertically oriented embodiment of FIG. 10 is shown as having a head end 20g and a cylin ⁇ drical baffle 62 disposed in the oxidizer inlet 12g to act as a flow diverter, ensuring that the oxidizer flow has an axial component directed only toward the head end, as shown by the arrows 64.
• the inlet flow is, of course, adjusted to provide a desired stoichiometric ratio for generating combustible gas.
• the present invention represents a significant advance in the field of coal combustors.
• the invention provides a slagging combustor operating with desirable slag removal characteristics at a relatively low stoichiometric ratio, and therefore providing for reduced heat losses and increased efficiency.
• the combustor is easily adaptable to match the requirements of various downstream processes, such as MHD generators or processes requiring synthetic fuel gas. It will also be appre ⁇ ciated that, although specific embodiments of the invention have been described in detail for purposes of illustration, various modifications may be made without departing from the spirit and scope of the invention. Accordingly, the inven ⁇ tion is not to be limited except as by the appended claims,

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• 1982
  • 1982-03-11 EP EP82901239A patent/EP0073830B1/en not_active Expired
  • 1982-03-11 IL IL65224A patent/IL65224A0/xx not_active IP Right Cessation
  • 1982-03-11 WO PCT/US1982/000311 patent/WO1982003261A1/en active IP Right Grant
  • 1982-03-11 JP JP57501243A patent/JPS58500420A/ja active Granted
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  • 1982-03-15 CA CA000398337A patent/CA1181998A/en not_active Expired
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