METHOD AND APPARATUS FOR DETERMINING THE VOLUMETRIC HEAT CONTENT OF GASEOUS FUELS

Abstract: An apparatus and method for determining the heating value of gaseous fuels includes a mixing device (60) for estab­ lishing a mixture of air and the gaseous fuel of interest in known volumetric proportions. An electrochemical sensor (48) senses the products of combustions of the precise vol­ umetric mixture and the output signal of the sensor is indica­ tive of the relation of the mixture to a stoichiometric mixture of fuel and air. This signal is used for adjusting the proportions of fuel and air in the mixture of interest until the sensor indicates that the mixture of known proportions is substan­ tially stoichiometric. A microprocessor (70) determines the heating value of the fuel from a known relationship between the heating of the constituents of the fuel and the amount of oxygen required for stoichiometric combustion.

Description: METHOD AND APPARATUS wOR DETERMINING THE HEATING VALUE OF GASEOUS FUELS Field of the Invention The present invention relates generally to the field of measuring and monitoring the heating value of gas eous fuels such as natural gas and, more particularly, to a method and apparatus for determining the heating content or calorific value of such fuels from a determlnatlor. sbstan- tially at the stoichiometric point of combustion of unknown mixtures containll.y precise volumetric proportions of fuc-i and air. DESCRIPTION OF THE PRIOR ART The heating value of gaseous fuels surn as natural gas are frequently given assumed average numbers. Thus, tne heating value of natural gas, for exarple, is frequently assumed to be 1000 British thermal units (BTU's) per cubic foot. In the past, pricing of such fuels has beer. based -r0' either the assumption of a nominal average value c the periodic checking of the actual value by a variety of time-consuming methods. In one method chromatographic analysis of tne constituents has been used to compute the actual heating value or BTU content of a given natural gas from the per centage composition of the mixture. In another method, the heat content has been determined by measuring the amount of heat liberated in burning exactly one cubic foot of gac (saturated witn water) at standard conditions of terperature and pressure. The heat so liberated is absorbed by a weighed amount of water and the subsequent temperature rise of tne water used to calculate the "gross or (night) heating value." This "calorimeter bomb" approach, like tE.e chromatographic approach, has several drawbacks. Both methods involve reasonably expensive instrumentation and require considerable labor to perform the measurements and calculations. Such testing also, of necessity, introduces considerable time delay and certainly appears less desirable than an on-line system. Even sc, these might be sufficient methods lf, in fact, the coci- tion of the gas being used did not vary greatly with tire. However, the composition of natural gas, for example, ray vary greatly in composition depending on the gas field rrcm which it came and the treatment it receives before dlsirlbu- tion. The gas that reaches the customer or consumer is fre ntly only about 85 percent methane with the rerairin 15 percent being a mixture of various hydrocarbon molecules such as ethane, propane, n-butane, i-butane, etc. Also, as much as 25 percent of the gas reaching the customer may be made up of non-combustible constituents which occur naturally or have been added to the mixture. These include nitro gen, air, and carbon dioxide. Natural gas is used herein as a representative example because it is by far the most widely used gaseous fuel. The inerts, of course, add nothing to the heating value, and the heating value of alkane and other hydrocarbons of a higher order than methane have a higher heating value on a volumetric basis because of their higher molecu- lar weights. In view of the great variation in constituents of natural gas, the heating value even in a single distribution system may vary greatly with time. In addition to the other variations, numerous gas utilities have found that in severe winter weather it is cost justified to add a mixture of propane and air to the fuel in order to meet peak demand. They have found that the increased cost of propane at such peak load periods is less than the cost of additional distribution capacity which would otherwise be necessary to meet the peak loads with gas that cannot be stored as liquid adjacent to users. As a result of all these factors, a random sampling of the heat content of the natural gas being distributed, might lead to great inaccuracies as to tnc- actual heating value of the fuel oelivered. linus, it is necessary for the heat content of the natural gas to be continually monitored and adjusted in order to stay within promised specified limits and to assure that the user is charged for the proper amount of heating value he receives from the fuel. Other incentives are involved in the desirability for providing an efficient on-line device for monitoring tr, heating value of gas. Users, especially those in industries, which require large amounts of gas for heat processing equipment can utilize such data to adjust ga input modes to provide a more uniform total heat input. They can also utilize such information to adjust burner controls so as to provide the proper air-fuel ratio and thereby avoid inefficiencies which occur when the burners are operating at a ratio which is either too lean or too rich. Attempts have been made to provide "on-line" devices. In the prior art it is generally Known tnat tne heat content of a gaseous fuel such as natural gas is reiated to the ratio of fuel to air necessary for complete corbustion of the gas. One prior art device utilizes a syster in which the heat content of the fuel is related mathe..2.i- cally to that ratio of air to fuel which maximizes tne adiahatic flame temperature of the mixture. In that syster the air and fuel are split between two bules in such a way that the mixture in one burner has a slightly higher air-fuel ratio than the other. The air flow is allowed to remain constant, and the fuel flow is varied in the two burners until the temperature of both flames is the same. In this manner, one burner approaches the maximum flame temperature from the "rich" side and the other from the "lean" side. The fuel flow is metered as by a turbine meter, and, based on the metered rates of air and fuel, a BTU heat content is calculated assuming the maximum adiabatic flame tern- perature occurs at the stoichiometric point of the combustion mixture. Actually, the maximum flame temperature may be reached when the mixture is somewhat lean, i.e. when an amount of excess air is present. A prior art method of calculating the heat content from such measurements is found in "New Approach to tne Continuous Measurement of Calorific Values of Gaseous Fuels" b William H. Clingman, Jr., AGA Operating Section (1972). That system has the drawback that it requires both accurate fuel measurement and temperature measurement of two complete burner systems for comparison. The use of electrochemical cells as oxygen or combustibles sensors to sense the residual products of co- bustion including electrochemical cells based on ceramic compounds such as ZrO2 is also known. Under normal conditions, natural gas is burned with an excess of oxygen to assure complete combustion and an absence of carbon mon- oxide in the products of combustion. This leads to the presence of an amount of excess oxygen after combustion which raises the possibility that an oxygen sensor based on zirconia or the like could provide a relatively inexpensive and rapid solution to the problem of determining heating values for natural gas mixtures based on the air-fuel ratio. Such solid electrolyte-based oxygen sensors have been used to rapidly provide information for such systems as catalytic automobile exhaust control. Several different types of solid electrolyte-based oxygen sensors are commercially available. Thus it has been proposed to use a ceramic based electrochemical made chiefly of zirconia (zoo2) which is known to exhibit a Nernstian voltage output when exposed to differing partial pressures of oxygen on each side of the ceramic material. This can be used to sense the amount of oxygen present in the products of combustion. That system proposes to utilize a known mass ratio between the fuel and oxygen supplied to a burner in conjunction with the measurement of excess oxygen after combustion using the Nernstian relationsip to provide a basis for deriving the heat co- tent of the fuel. According to that system, measurements should be made when the combustion mixture contains about 2c percent excess air, that is, not stoichiometric combustion. That system requires that the air and fuel be controlled so as to be measured in relation to standard terperature and pressure and precise metering of the mass flows of fuel and air. Also the sensor output is decidedly tem- perature sensitive in the presence of more than minute amounts of oxygen. Thus, when operating in the oxygen-rich portion of the ZrO2 electrochemical response curve, the tenperature of the sensor must be carefully controlled. Unfortunately, the system does not take into consideration the fact that as the heating value of the gas to be measured increases, so does the average molecular weight of the gas. While this could be overcome with appropriate correction factors, if only combustible gases were involves, the molec- ular weight of the fuel species can also be varied because of the presence of inert species in the mixture which leads to calculation errors. SUMMARY OF THE INVENTIGN According to the present invention, the problems associated with prior art attempts at on-line measurement of the heat content of gaseous fuel are substantially solved = the provision of a unique heat content measuring system which utilizes a ceramic electrochemical oxygen sensor in a manner which eliminates both the need for precise temperature control of the sensor and errors introduced by inert constituents. The heat content measuring system of the present invention includes an accurate volumetric measuring system to accurately proportion the fuel which is mixed: air. A single sample burner in combination with the sensing system provides the necessary air-fuel information necessary to the heat content measurement of the fuel gas of interest. The system is designated to control combustion at the stoichiometric point (FIGURE 18) wherein the electrochemical sensor exhibits a step-change function to produce increased accuracy. At this point, the precise volumetric ratio of fuel to air is accurately known from the measuring system and the heat content of the fuel can be accurately determined from that ratio in a manner simplified by the elimina- tion of the effects of several undesirable variables. The fuel heat content metering system of the present invention includes a precise, adjustable metering system which accurately proportions an amount of fuel gas or calibration gas to be tested with a known amount of air such that at any given time, the volumetric ratio of air, and therefore, to fuel is precisely known. The mixture is fed to a burner system in which the fuel is combusted in the presence of a solid state ceramic electrochemical cell whit. provides a step-change in voltage output as tne amount of residual oxygen or combustibles approaches zero, that is, approaches the point of stoichiometry. An electrical signal from the electrochemical cell is utilized with a programmable electronic processing system to adjust the fuel mixture in accordance with the output of the electrochemical cell to achieve and determine the stoichiometric air-fuel ratio as signally by the rapid change in electrical output of the cell at that point. The air-fuel ratio at that point is known from the measuring system and the heat content of the fuel is readily determined therefrom. In the preferred embodiment, the metering of tne fuel and air is accomplished by one of several alternate, novel systems which provide precise, time proportioning vo- umetric measurement. In one embodiment of the proportioning system of the invention, fuel and air are fed through a rotary valve system in which the proportion of air or gas transferred therethrough to the combustion chamber deeds on the speed of rotation of the rotary valve. The rotating member contains hollow chambers which are alternately filled with fuel and purge with air as they are rotated in tne fashion of a Gatling gun. The air flow remains constant and the fuel introduced varies with the angular speed of the rotor. A motor, the speed of which can accurately be controlled, as with a stepping motor, is provided to allow for a great deal of flexibility in adjusting the rotation speed and thus the air-fuel ratio. In an alternate embodiment of a proportioning system, fuel is fed to a mixing chamber alternately through each of two separate series of valves such that precise known amount of fuel contained in a cylindrical chamber between two valves in each series is ultimately pushed irt the mixing chamber by a constant regulated air flow. While one series is connected to the burner, the cylindrical charber of the other series is being refilled-with the fuel gas. The system is switched in a time sequenced manner to alternately connect one valve series then the other to the measuring burner system. The air-fuel ratio is readily varied merely by adjusting the cycle time of the system. Inasmuch as fuel and air are fed to the measuring burner at the same regulated pressure and, if packaged together, will be at or close to the same temperature, this eliminates the additional variables relating to differences in temperature and pressure which otherwise would have to be compensated by measuring the temperature and pressure and adjusting the calculation therefor. Temperature and pressure compensation, of course, may be provided in the fuel and air supply for applications wherein the keeping of equal pressure and temperature is not practicable. Because precise volumetric measuring is used, the need for compensating for changes in molecular weights of combustibles or for the addition of inert components is also eliminated. Calculation of heat content is made utilizing a microprocessor system from a simplified known constant rela- tionship between the air-fuel ratio at the stoichiometric point which is known from the speed of the sampling system and the corresponding fuel heat content. The results may be rFrordPd or displayed in any manner desired. The heat given off by the combustion of the given mixture can also be utilized to maintain the temperature of the electrochemical cell within the desired range. In the preferred embodiment, the cell within the desired range is a ceramic cell primarily made up of Zr02 stabilized with an amount of CaO, MgO, or Y203, to stabilize its temperature related response such that in the step-change portion of t sensing curve, the cell is repeatably accurate without tem- perature compensation from about 6000F to 1,4000F (315 to 77O0C) BRIEF DESCRIPTION OF THE DRAWINGS In the drawings wherein like numerals are used te designate like parts throughout the same: : FIGURE 1 is a perspective view of a mounted in-line instrument utilizing the invention; FIGURE 2 is a schematic block diagram of the preferred embodiment of the invention; FIGURE 3 is a schematic block diagram of an alternate embodiment of the invention; FIGURE 4 is an view partially in section of a rotary valve system of the embodiment of FIGURE 2; FIGURE 5 is a reduced, exploded view of the roar valving system of FIGURE 4; FIGURE 6 is an enlarged view of an alternate rcta- ry valving system of the embodiment of FIGURE 2; FIGURE 7 is an exploded view of the rotary valvl.,c system of FIGURE 6; FIGURE 8 depicts the layout of the multi-sheet FIGURES 9, 10, 12, and 14. FIGURE 9 is an electrical block diagram of the embodiment of FIGURE 2. FIGURE 10 is a diagram of electrical details of the diagram of FIGURE 9. FIGURE 11 is a block diagram of the logic diagrams of FIGURES 12-17; FIGURE 12 is a logic diagram for the main routine system of FIGURE 11; FIGURE 13 is a logic diagram for the startup tacr. of FIGURE 11; FIGURE 14 is a logic diagram for the search task of FIGURE 11; FIGURE 15 is a logic diagram for the calibrate task of FIGURE 11; and FIGURE 16 is a logic diagram of the display task of FIGURE 11; FIGURE 17 is a logic diagram of the read temperature task of FIGURE 11; FIGURE 18 is a representative curve of the response in millivolts versus the air fuel ratio of a typical Zero2 sensor in accordance with the invention. FIGURE 19 is a plot showing heat content of various hydrocarbon fuels. DESCRIPTION OF THE PREFERRED EMBODIMENT The heat content measuring system of the present invention contemplates a simple, accurate method and apparatus for determining the precise ratio of air to fuel in a combustible mixture which can be utilized, in turn, to accurately determine the heat content of the fuel used. This system does not require remote sampling and can actually be used in an on-line manner. As will be seen from the detailed description, substantially all of the sources of error introduced in previous attempts to achieve accurate on-line readings have been substantially eliminated. In FIGURE 1, there is shown generally at 20 a. in situ placement of a heat content measuring device in accordance with the present invention. Thus, the device can be mounted on a fuel line 21 and connected to it as by a sample line 22 such that continual on-line measuring of the fuel passing through the line 22 can be achieved. As depicted in FIGURE 1, the apparatus may have an explosion proof case having halves 23 and 24 securely bolted together. Ventir.- is provided as at 25. Typical adjustment knobs 26 and 2; corresponding to display readouts 28 and 29 are represented which may read out directly in air-fuel ratio, 8TUs, or calories, or any other convenient units of measurement. FIGURES 2 and 3 depict alternate embodiments cf the heat content measuring system of the invention. The system of FIGURE 2 includes an air supply system, both calibration and unknown or sample gas supply systems, a mixing system or proportioning system, and a combustion and measuring system. In FIGURE 3 there is shown an alternate embodiment to the system of FIGURE 2 in which an alternate type of proportioning system is utilized. The preferred embodiment is shown in FIGURE 2. This includes an inlet sample fuel gas line 30 which includes corresponding filter 31, pressure regulator 32, and orifice 33, and, similarly, for the calibration gas system there is an inlet line 34, filter 35, regulator 36, and metering orifice 37. The lines 30 and 34 converge upon a three-way valve 38. Similarly, air is provided in line 39 by blower 40 with filter 41! associated pressure regulator 42 and metering orifice 43. A sample or main combustion chamber is provided at 44 with burner 45, flame safeguard unit 46 with associated flame igniter-sensor 47 and the electrochemical combustion product sensor 48. Contact 49 associated with the main safety shutoff valve 50 is provided to shut off the fuel flow should a flame out or other problem occur. Similarly, an auxiliary contact 51 is provided for external use, also controlled by the main burner flare safeguard system 46. A flare and vent system is provided with combustion chamber 52, burner 53, flame safeguard unit 54 with its associated igniter-sensor 55. The main ar. flare combustion chambers are connected to their associated flame safeguard systems by conductors 56 and 57 respectively. The lines 56 and 5; also represent 16 conductor for the spark ignition in this schematic drawing. Additional components include an air temperature sensor T1 and fuel mixture temperature sensor T2 with respective associated leads 58 and 59. The embodiment of FIGURE 2 introduces a completely distinct and unique proportioning and mixing concept including a rotary mixing valve 60 driven by an associated motor 61. The rotary valve is supplied by the gas of enter est by line 62, and air by line 63. The proportional mixture is conveyed to the main burner by 64 and residual fue to the vent burner by 65. The operation and details of tne mixing system 60 and associated motor 61 will be described in greater detail with reference to the alternate eodi- ments thereof shown in FIGURES 4-9. The main electrical components which will be described below are shown in block form in FIGURE 2 and include a conventional microprocessor control board 70. Temperature information on lines 58 and 59 is processed by an analog-to-digital converter 71 and supplied to tne control board by 72. Flame safeguard information is received on lines 73 and 74 and information from the sensor 48 on line 75 via a threshold detector 76. Various other inputs are received at 77. A display 78, alarm 79, and printer etc receive information from the board 70 along respective routes 81, 82, and 83. In FIGURE 4 there is pictured one embodiment or a rotary valve proportioning system in accordance with 60 of FIGURE 2. The internal structure of the system is depicted in greater detail in the exploded view of FIGURE 5. Tne basic components of the rotary valve system include the motor 61, the proportioning distribution rotor 100 flanked by a distribution plate 101 and an end plate 102. The shaft 103 of the rotor 100 is coupled to the shaft 104 of the motor 61 as by a flexible coupling 105. The end plate 102 is spaced from the motor mounting face plate 106 and secured thereto as by a plurality of radially distributed bolts 107 secured as by nuts 108 and 109. As can more adequately be seen in FIGURE 5, the threaded bolts 107 are of such a dla.- eter as to pass through holes 110 in the member 101 such that the plate member 101 is free to slide along the axes of bolts 107. The rotor member 100 is provided with flanking seals 111 and 112 and the entire assembly including the rotor 100, distribution plate 101, and end plate 102 wit the seals 111 and 112 is held in place as by a helical spring 113 which pushes on the members 101 and 106 to hold member 101 in position at the desired pressure. The fuel inlet line 62 and air inlet line 63 are connected to the member 101 as by fitting at 114 and 115, respectively. The mixture to be combusted or vented leaves the mixing system. as via fittings 116 and 117 connecting lines 64 and 65. By means of the rotary mixing system depicted in FIGURES 4 and 5, air and fuel enterinq the system is precisely proportional in a unique manner. As seen in FIGURE 5, the distribution member 101 is provided with an elongated partial annular groove or slot 118 and a shorter partial annular groove or slot 119. Both slots 118 and 119 may be of square section or semic:rcular section as desired. (It should be noted that the single member 101 in FIGURE 5 has been flipped over or rotated 180 with respect to the othrr members of the exploded view to expose the internal slotteo or grooved structure of the member). Corresponding grooves 120 and 121 are provided in the member 102. The rotor member 100 is provided with a symmetrical pattern of radial ly distributed holes 122 which cylinders of known volume extending through the member 100, and the seal members 111 and 112 are provided with a similar pattern of holes designated 123 and 124, respectively. Seals 111 and 112 are provided with a series of alignment holes as at 125 which fit over machined pegs as at 126 in the rotor member 100 to assure proper alignment of the seals with the rotor 100 such that the patterns of holes are aligned internally to connect the grooves 118 and 119 with the grooves 120 and 121, respectively. Inlet holes or parts 127 and 128 connect the grooves 118 and 119 with the respective air and fuel inlets at 115 and 114. Outlet holes or parts 129 and 130 connect with outlets 116 and 117, respectively in a like manner. In this manner, the fuel in line 62 passes into the groove 119 and the eir from conduit 63 passel into the groove 118. Thus, the groove 119 at all times is open to incoming fuel, and the groove 118 at all times is open to incoming air. When the motor 61 is energized, the rotor 100 and associated seals 111 and 112 are rotated with the motor shaft speed. This causes the hole systems of the rotor member 100 to alternately be exposed to the fuel of groove 119 and air of groove 118. The grooves 120 and 121 with associated outlet ports 129 and 130 therein are always connected respectively to the mixture outlet lines 64 and 65. In operation, amounts of regulated air and sample or unknown fuel gas of interest are fed to the inlet conduits 63 and 62 and the motor 61 which is preferably a stepping motor is energized through the electronic system which includes a stepping motor drive control (discussed in detail below in conjunction with tne discussion with the electronic system). As the shaft of the stepping motor rotates1 the direct coupled rotor 100 of the air-fuel proportioning system also rotates at the same speed. The air groove 118 in the distribution member 101 is continuously supplied with air, the groove 119 is continuously supplied with sample. Rotation of the member 100 together with the aligned seals 111 and 112 aligns and connects each of the cylindrical passages 122 alternately with the groove 119 and the groove 118. The members 101 and 102 are disposed in fixed alignment such that the corresponding air grooves 118 and 120, and the fuel grooves 119 and 121 face each other through the rotor 100. Thus, any given port 122 aligned with the supply groove 118, of course, connects to the outlet groove 120 such that during this time, the contents of any aligned cylinder are caused to flow into the outlet groove 120 and through the port 129, and the corresponding hole 122 is filled with air. Upon reaching the position of the aligned grooves 119 and 121, the port is then exposed to the sample fuel, and the air is expelled or pushed out through the port 130 and the cylinder 122 filled with the sample fuel such that when the angular displacement of the particular cylinder 122 again aligns with the grooves 118 and 120, the fuel will be displaced by air with the fuel being dispensed through the port 129. As can be seen in FIGURE 5 the annular air grooves 118 and 120 are much longer than fuel grooves 119 and 121. Nominally the air grooves may encompass about 240 and the fuel grooves 60 with two 30 spaces therebetween. This allows for the continual passage of an amount of air throw the system. It can also be readily seen that the ratio of fuel to air reaching the groove 120 and passing throu the outlet port 129 and eventually the burner 45 (FIGURE 2) will hp directly proportional to the angular speed of the rotor 100. The faster that the rotor rotates, the higher the proportion of fuel to air that will be passed into the main combustion system. So far as the mixture vented through the opening 130 through conduit 65 is concerned, the theory of "plug" flow would dictate that since the fuel which had been pick up by any given cylindrical volume chamber 122 would have been exhausted at the groove 120, only air would be exhausted through the vent at 65. In reality, however, because of some diffusion mixing, the gas is not entirely purged from each of the cylindrical volumes 122 of the rotor 100 such that a minute amount of residual fuel is expelled in the mixture at outlet opening 130. This adds to the overflow of the supply gas which is sufficient to sustain the small vent burner or flare 53. If necessary an auxiliary supply line (not shown) may be provided from the sampling system inlet line 62 in a well known manner to sustain the flame in the burner 53. The inlet and outlet ports connecting the grooves are preferably located at the extremes of the grooves in either embodiment. In the case of the fuel system, the inlet of the shorter groove should be at the point last encountered by the rotor and the effluent exit should be at the end of the groove or slot first encountered. In tis manner, the fuel tends to flow through the supply slot and the effluent through the exit slot in a direction opposite to the direction of rotation of the rotor member. The inlet and outlet accesses for the air and mixture of interest, the inlet should be at the extreme first encountered by the rotor and the mixture outlet at the extreme last encountered by the rotor such that the air tends to flow in the same direction as the direction of rotor rotation. This enhances the operation of the system to achieve improved purging and mixing. The important point is the fact that equilibria is soon reached and precise repeatable desired ratios of fuel to air can be obtained through the outlet opening 129 such that the mixture at the main burner 45 may be precisely controlled in accordance with the speed of the rotor 100. This, in fact, is accomplished with a great degree of acc- racy. The air, of course,- continually flows through the system as there are always cylindrical volumes 122 connected between the air supply and the outlet to the main burner 4; through the rotor 100. An alternate embodiment of the rotary air-fuel proportioning system 60 is shown in FIGURES 6 and 7. inns embodiment may be interchanged with the previously described embodiment 60 in fuel heat content measuring system of FIG URE 2. In FIGURE 6 there is shown an elevational view o the alternate embodiment of the rotary valve, the exploded de.d,ls of which are shown in FIGURE 7. This system includes a motor 140 similar to 61 which may have an integral base 141 with mounting holes 142, air-fuel distribution stator member 143, a rotor member 144 with associated plate 145, and a cover member 146. The stator distribution member 143 is provided with annular disposed recessed grooves or slots. These include longer slots 147 and 148 and shorter slots 149 and 150 which may be recessed in the surface in a shape rectangular or semicircular in nature as with the slots of the embodiment previously described. Four access ports are provided from the circumference 151 of the stator distribution member 143 at 152-155 which may be in the forr of radially disposed drilled holes which are located below the bottom of the grooves 147-150 and connected to the respective grooves as by four holes in the base of the grooves as at 156-159. The access ports 152-155 are then respectively connected as by four inlet elbow pipe fittings 160-163 as shown in FIGURE 7. In this fashion, inlet fitting 160 is directly connected with to the groove 147, outlet fitting 161 to groove 148, inlet fitting 162 to groove 149, and outlet fitting 163 to the groove 150. The rotor member 144 is provided with two concentric, symmetrically distributed series of radially disposed holes 164 aligned radially in pairs. The member 145 is provided with a series of radially disposed recesses in tnc form of grooves or slots 165 such that when the relative positions of the rotor 144 and member 145 are in proper alignment, each of the radial pairs of holes 164 aligns with a recessed slot 165 therewith forming a "U" tube of defined volume. The members 144 and 145 are secured together as by screws or bolts at 166. When assembled, the hollow shaft 167 of the rotor member 144 is keyed to and receives the motor shaft 168 and is secured thereto as by set screws at 169. Access to the set screws may be provided as by an additional radial opening 170 beneath the grooves in the face of the stator distribution member 143. The unitary structure including members 144 and 145 is adapted to be received in the recess 171 of the cover member 146 such that it is free to rotate therein. However, the smallest practical clearance should be maintained between the rotating structure front face 172 and the front face 173 of the stator member 143. This assembly is bolted together as through holes 142 in motor mount 141 to stator 143, and through holes 174 in cover 146 to stator 143 to secure the assembly together with the un!tary structure including combined members 144 and 145 frec to rotate with the motor shaft within the assembled housing in extremely close proximity to the member 143. In this manner, a series of radial "U" tubes are provided connecting the inner and outer grooves of the stator 143. The fittings 162 and 163 are connected to furl 1; dnd fuel out or vent lines corresponding to lines 62 and 65 of FIGURE 2. Fittings 160 and 161 are respectively connected to incoming air and precisely-ratioed mixture lines as at 63 and 64 of FIGURE 2. One successful embodiment utilized 12 U-tubes syr- metrically radially distributed in the combined rotor member which yields a 30" separation. The shorter slots 149 and 150 in the stator member 149 subtended an angle of 60" and the longer grooves or slot members 147 and 148 subtended an angle of about 240 of the circumference of the member 143 with 30 separating both extremes of the grooves. This, of course1 means that at least two of the "U" tube members will always be aligned connecting the slots 149 and 150 and at least eight "U" tube members likewise will always connect the corresponding slots 147 and 148 at any given instant in time no matter what the relative rotation position of the combined member 144-145. The operation of the proportioning system of this embodiment is easily described by selecting any "U" tube system and following its progression as it rotates about in the system. At some point in time, a given "U" tube will encounter the fuel section of the system connecting slots 149 and 150 such that regulated volumetric flow of fuel flows through the opening 158 filling and purging the slot 149 and the given "U" tube, also purging and filling the slot 150 and finally leaving through opening 159 and fitting 1 into the vent or flare gas line to be vented and burned at 49 in FIGURE 2. The fuel flow rate, highest anticipated motor speed, and "U" tube volumes are sized such that for any reasonably anticipated stoichiometric air-fuel ratio, the "U" tube will be completely filled with fuel and all the sir expelled during the interval in which it connects the slots 149 and 150. Continued rotation brings the "U" tube across a 300 blank section of the stator and the metered fuel in the "U" tube remains trapped therein. As the fuel filled "U" tube is exposed to the 240G segment of slots 147 and 148, air is allowed to enter at the controlled volume ric flow rate and proceeds through the system. During this interval the U-tube connects slots 147 and 14± such that air entering the pipe fitting 160 pushes the fuel contained in the "U" tube into slot 148 and eventually out through the radial hole 153 and fitting 161. The fuel, now mixed with air, proceeds as through line 64 in FIGURE 2 to the sample or main combustion burner 45 where it is burned in accordance with the present invention. From the configuration, it can be seen that eight "U" tubes are exposed to air simultaneously and that the mixture in line 64 will be a mixture of the flows from all eight "U" tubes. It can also readily be seen that the air flow supplied to the combustion chamber through the rotary proportioning system is totally independent of the rotary valve operation inasmuch as there are always the same number c= U-tubes supplying air. The fuel flow rate, on tne other hand, is determined by the frequency at which "U" tubes are filled and flushed by the air, that is, the rotational speed of the valve and the volume of the "U" tube. Of course, the U-tube volume is constant for any particular device. Therefore the air-fuel ratio at the burner 45 will be directly proportional to the speed of the rotary valve within the limits stated above. In FIGURE 3 there is shown an alternate embodiment to that of FIGURE 2 which is similar except for the proportioning system. The sample gas inlet system for that embodiment is similar including a supply line 200 which leads successively to a filter 201, pressure regulator 202, and metering orifice 203, and inlet valve 204. Likewise, a calibration gas system may be similarly provided for calibrating equipment including an inlet line 205, filter 206, regulator 207, and orifice 208. The air inlet system includes a supply of air as from blower 209, pressure regulator 210, and metering orifice 211, supplying air to inlet line 212. The valving system of the air-fuel proportioning system includes three-way valves 213, 214, 215, and 216. These are joined together as shown by cylindrical chambers 217 and 218 and conduit lines 219, 220, and 221. The system is connected to a mixing chamber 222 by conduit 223 anc, in turn, the mixture is introduced to combustion chamber 224 by conduit 225. Further lines 226 and 227 lead to a vent or flaring combustion chamber 228. The measuring or main combustion chamber contains a burner 229 and a electrochemical sensor 230 along with an igniter flame safeguard device 231 with associated flame sensor-igniter 232. Likewise, the vent or flare combustion system at 228 also contains a burn er 233, associated safeguard device 234, and associated sensor-igniter 235. In normal operation the gas of interest enters as through the conduit member 200 which may be permanently attached to a fuel line, or have other means for temporary connection to a source of sample fuel gas, the heat content of which is to be measured. As with the preferred embodiment, the gas passes through the filter 201 and the pressure and flow rate are regulated by regulator 202 with orifice 203 adjusted to give the desired flow rate. When used, the calibration gas enters the system in the same fashion at 205. The three-way valve 204 is normally in the position such that the fuel gas of interest will enter tne system through ports A and C. Port B is shut off thus isolating the calibrating gas. During calibration of the instrument, the valve is switched either manually or automatically to allow calibration gas to enter through ports B and C with port A shut off thus isolating the sample gas. Likewise, air provided by the blower 209 is regulated in flow and pressure by the regulator 210 with orifice 211 and cnters the system through line 212. The proportioning system of this embodiment of the invention is provided by the combination of four three-way valves 213-216 in conjunction with cylinder sections 217 and 218 which are of a precisely known volume. The three ports of each valve have been designated by the letters A, B, or C. If we envision each of the valves as being in one of two possible positions, we can designate the system position I to be one in which all ports designated A are connected with all ports designated C and all parts B are closed. Witn tne system in position I, then, fuel in conduit 219 is directed through valve 213 into and filling the cylinder 217, through valve 214 into line 227 and vented through the venting burner system at 228. Simultaneously, air proceeds from line 220 through valve 215 filling cylinder 218 and is exhausted through valve 216 and lines 221 and 223 into the mixing chamber 222. When the position of the four valves 213-216 are switched, all ports labeled B and C are then connected. This can be designated position II. With the system in position II, fuel flows from line 219 through valve 215, cylinder 218, valve 216 into the vent gas system, and, conversely, the air flow is through valves 213 and 214 and again into the mixing chamber 222. It can be seen from FIGURE 3 and the above description that in position I, with all ports A and C cos ëcted, only the precise amount of gas contained in cylinder 218 between valves 215 and 216 is pushed by air from conduit 220 into the mixing chamber 222. The remainder of the flow is air. Simultaneously, fuel gas is filling the cylinder 217 between valves 213 and 214 with all the excess being vented through the vent burning system at 228. In position II, the precise opposite is true with the air pushing the precise volume filling cylinder member 217 between valves 213 and 214 into the mixing chamber while t cylinder 218 between valves 215 and 216 is refilling with the fuel gas. In either case, all the excess fuel gas is vented through the vent or flare system 228 and all the air, in either position, in goes to the mixing chamber 222. Therefore, as the four valves 213-216 switch alternately between positions I and II, etc., precise amounts of fuel contained in the cylinder sections 217 and 218 between the respective valves are alternately pushed into the mixing chamber by the air supply. The air and fuel mixes in the chamber 222 and proceeds through conduit 225 into the measuring or main combustion chamber 224 where it is combusted by the burner 229 and the products of combustion are sensed by the electrochemical cell sensor 230. As will be described in greater detail below, the signal from the electrochemical sensor on line 240 proceeds to the signal processing electronics. The air-fuel ratio eminating from the mixing cha- ber 222 to te burner 229 may be precisely varied simply by modulating the switching frequency of the four valves 213-216. This is accomplished in a well known manner through a multiplexing system with associated electronic signal processing means. Thus, as the frequency of the valve switching increases more volumes of gas of interest from the cylinder sections 217 and 218 are caused to enter the mixing chamber during any unit amount of time. Because the mixture supply is constant, this enriches the mixture. Conversely, if the frequency is decreased, the mixture becomes more lean. The only limitation, of course, is the switching ability of the valves and the corresponding volumes of the cylinder members. If the volumes of tne cylinders 217 and 218 are kept small, the frequency which the system can be switched is limited only by the response time of the valves 213-216. It is also desirable to keep the mixing chamber 222 small so that the gas being burned at the burner 229 taKes less time to reach an equilibrium mixture at a given switching rate. It should be noted that provision may be made to compensate for differences in the inlet temperature and fuel gas of interest. A temperature sensor T1 with corresponding signal conductor 241 may be provided to sense the temperature of the air admitted to the system and a second sensor T2 with lead 242 to measure the mixture temperature. Ine signals on 241 and 242 can then be used to apply any re volumetric correction to the fuel proportion in accordance with the gas laws in a well known manner as described below in relation to the preferred embodiment. In accordance with the embodiment of FIGURE 3, the valves 213-216 may be any high duty cycle, electrically switched valves such as poppet valves. Valves which have been successfully used include Model S4Pl8C2B manufactured by Valcor Engineering Corp. of Kenworth, New Jersey, which have an approximate switching time of S-86. In accordance with either the embodiment of FIGURE 2 or FIGURE 3, the pre-mix burner which does not require secondary or atmospheric air to operate properly and which will function at the desired flow rate. The vent gas burners may be any conventional atmospneric burner such as a Bunson burner. It has been found that during the operation of the system the burner flame will be sustained by the vented effluent gases. However, provision may be made for auxiliary fuel and air to be supplied from the system if desired. The flame sensors and flame safeguard units are highly conventional and readily available commercially as a model S-86 manufactured b a assignee of the present invention. In either embodiment, the pressure regulators may be any accurate low flow, low pressure regulators such as 912 series pressure regulators available from the Fisher Controls Company of Marshalltow,., Iowa. The main burner of either embodiment is typically operated at s pressure of about 2,5 bar. w.c. and a firing rate of about o,17m3/h of mixture. As can be seen from the above, the valving system depicted in FIGURE 3 along with the rotary proportioning systems of FIGURES 4-5 and 6-7 provide accurate, predictable means for combining two fluids in any desired proportion. The proportion can be determined simply from the rotational speed of either alternative embodiment of the rotary valve or by the switching speed of the valving system of FIGURE 3. Of course, the embodiment of FIGURE 3 also has interface with the electronics of the system in a similar manner as the embodiment of FIGURE 2. Likewise, sensor 230 is provided with an electrical lead 240 and flame safeguar units 231 and 234 provided with leads 243 and 244, respectively. As is well known in the art, the open-circuit voltage of a simple electrochemical cell is established by a chemical potential difference which may be based on coposi- tion, concentration, pressure, etc., between the anode and the cathode compartments. The particular species to which the cell is sensitive is the same for both the anode and the cathode compartment, the open-circuit voltage should be zero. If, however, one of the electrode compartments is exposed to a reference quantity of the specie of interest and the other electrode exposed to a medium containing a different amount of such specie, an open circuit potential ditterence is thereby established. Various ceramic compounds are known to establish such electrochemical cells in the presence of differing amounts of oxygen. In the preferred embodiment of the present invention, a modified compound consisting essentially of zirconium oxide (or02) is utilized as a ceramic-based electrochemical cell for the sensor. The electromotive force of the cell is created by exposing one of the electrodes to a medium containing a reference amount of oxygen, namely air, and the other to the products of combustion of the sample fuel of interest in the sample combustion chamber. Thus, when the oxygen concentration in the combustion chamber differs from that of the reference air,- a potential difference is set up across the cell which can be measured and/or utilized in accordance with the present invention. The ZrO2 sensors of the present invention are normally stabilized with CaO, MgO, or Y203 which enhances the chemical and physical stability of the zirconium oxide for use as a sensor. The typical configuration of an electrochemical sensing cell in accordance with the present invention may be represented by 2r, Pt/Zr02 ' CaD/Pt, O2s where r stands for reference and s sensed or sample. Norse metal, normally platinum, electrodes are utilized in conjunction with the anode and cathode of the zirconium oxide sensor. As can be seen in the curve of FIGURE 16, in tne rich portion of the curve, which indicates the presence of excess combustibles, and in the lean portion of the curve (representing excess oxygen in the combusted gases), the curve does not change a great deal with respect to change in either the concentration of combustibles or oxygen but the center portion of the curve, however, which is close to the stoichiometric point or the point where the amount of oxygen present is Dust sufficient to oxidize the hydrocarbon components, the curve undergoes the step change function wherein the voltage output varies a great deal with very little change in oxygen concentration in the combustion chamber. It has been proposed to use the ZrO2 sensor in the lean portion of the curve to relate the partial pressure of oxygen present to the air-fuel ratio. As previously stated, as the amount of excess air increases above the stoichiometric point, a non-linear curve results. This portion of the curve has been found to be a Nernstian response region wherein the variation of the cell open-circuit voltage with the partial pressure of oxygen present at the measuring electrode is given by the well known equation: EMI34.1 wherein E is given in voltage units (volts) R and F are constants and T equals ;f absolute tetperature. It can readily be seen from this equation that the voltage output varies inversely with the natural logarithm of the partial pressure of oxygen in the combustion chamber and directly with the absolute temperature. Making use of data desired in this region of the curve, of course, requires very accu rate temperature and voltage measurements in order discern the applicable air-fuel ratio. Otherwise errors are easily introduced in the results. Unlike prior art systems which suggest measuring the residual oxygen in the Nernstian response region, t present invention contemplates utilizing the step response evident at or near the stoichiometric point in which the output of the cell varies greatly with an extremely small change in the air-fuel ratio. This rapid change is far easier to detect and more accurate utilize than are points in the Nernstian region. In either embodiment, when the mixture of sample fuel and air is combusted in the combustion chamber, the chemical composition of the combusted gas mixture is sensed by the modified zirconium oxide sensor thereby producing an electrical response in accordance with the curve depicted 1 FIGURE 16. When the mixture in the combustion chamber is such that the products and combustion approach stoichiometry either from the rich or the lean side, an extreme step change is noticed in the output voltage. This step change can be utilized as a control signal of stoichiometry whicn is repeatably precise and eliminates the errors associated with gradual changes in a curve. The use of stoichiometric point in the combustion of in the given alkane hydrocarbon fuel gas will now be more fully developed. The stoichiometric combustion equation for methane, the chief component of natural gas fuels, is given by the following equation which assumes that the air utilized for combustion comprises 20.83 percent 02 and 79.17 percent N2 and other inerts: : CH4 + 2(02 + 3.76N2)--, CO2 + 2H20 + 7.52N2 Therefore, wherein A/FCH4 represents the air-fuel ratio of methane A/FCH = (2)(4.76)/1 = 9.52 Table 1 represents stoichiometric air-fuel ratios of various alkane hydrocarbons through pentane and adds a column HHV which represents the higher or gross heating value of each particular specie in units of BTUs per cubic foot at 68OF, 14.7 PSIA which are derived MARKS Mechanical Engi- neering Handbook Seventh Edition. The HHV includes the latest heat of vaporization for steam formed in the cos- tion reaction. It should be noted that in deriving the actual air-fuel ratios, a value of 0 has been assigned to inerts which normally carry through the system unchanged and an arbitrary value of minus 4.76 has been assigned to each 02 based on its combination with alkane hydrocarbons in the combustion reaction. TABLE I SPECIE A/F HHVt CH4 9.52 994.7 C2H6 16.66 1742.6 C3H8 23.80 2480.1 C4H10 30.94 3215.6 C5H12 38.08 390.2 INERTS 0 0 02 -4.76 0 * BTU/FT3 AT 68F, 14.7 PSIA (MARKS) In view of the above, for a sample of mixed saturated alkane hydrocarbons, inerts and oxygen, the air-fuel ratio of a sample (A/F5) may be represented by A/Fs = 9.52x1 + 16.66x2 + 23.8x3 + 30.94x4 + 3E.08x5 - 4.76x7 wherein the x subscript represents the fraction of that hydrocarbon constituent having the given number of carbon atoms through 5 and the 7 has been assigned to oxygen. Tne higher heating value of the sample (HHVs) then can be gl;en by EMI37.1 As explained above, each of the fuel proportioning systems utilized in the heat content measuring system of the present invention depends upon displacing fuel by air from a hollow cylindrical or tubular member at a specific voluret- ric frequency and running air through the same cylinders for a certain amount of time all at the same controlled flow, that is air. For any of these cylinders, then, the cycle time (tc) can be represented by tc = ta + tf (I) wherein ta equals the time devoted to the passage of air and tf represents the time devoted to the passage of fuel. Thus, the time devoted to fuel, tf, can also be represented by EMI38.1 wherein Vi is the volume of any given cylinder and q equal the volume flow rate of air. Inasmuch as all the fuel lr. the system is pushed through the cylinder at the air flow rate, the air and fuel flow rates of flow must be identical on a time basis. Substituting for in equation (II), we have EMI38.2 Rearranging equation (III), gives us EMI39.1 Because of the identical flow rates as explained above, by definition EMI39.2 and, by substituting for ta by equation (IV) and for tf fror equation (if), we have EMI39.3 which, upon simplifying, yields EMI39.4 Also, as explained in conjunction with the description of the apparatus, above1 the volumetric flow rate of air ma be any arbitrary fixed rate established in the instrument çy pressure regulation, volumes, etc., and the volume of each cylinder utilized in the particular proportioning system similarly acts as a limiting constant. Given this situation, let EMI40.1 If we substitute kl for qa/V in equation VII, the result is A/F = Klte - 1 (IX) Returning again to FIGURE 19, by use of that figure, the following may be derived: : HHV5 = 103.68 A/F5 + 7.67 (X) A combination of equations (IX) and (X) thus yields HHV5 = 103.68 kltc - 1 + 7.67 which upon simplifying yields HHVS = 103.68 kltc - 96.01 (XI) Inasmuch as the instrument is utilized at a constant mixture flow rate and the volumes of the cylinders for a given instrument remain constant, the constant kl will be known and thus the HHV5 is rendered directly related to the cycle time of either the or the valving system utilized. A representative system operating control and measuring electronics implementation is shown in in FIGURES 9 and 10. FIGURE 8 shows the sheet layout for FIGURES 9 and 10. Thus, in FIGURE 9A, there is shown an analog board1 in FIGURE 9B, a microprocessor board, in FIGURE 9C, a gas supply and flame safeguard system. Some details of the analog board of FIGURE 9A is shown in greater detail in FIG URE 10. In FIGURE 9A there is shown the analog board P which includes an array of attached input thumb wheel switches as at 300 and indicates the connections with various other parts of the electronic system including the CMC 68/15 microprocessor control board of FIGURE 9B which is designated P'. The numbers and letters designated for the connection to P and P' constitute the pin connections to the board P and P'. A series of pins beginning with P9 and exit ing with P38 on board P are adapted to line up and connect with pins P'43-P'67 of the CMC 68/15 and the composite of these lines comprise the address and data buses therebetween. Thumb wheel switches associated with the hoard P are provided to enter data associated with various peripheral functions associated with a particular model of the invention. Thus, such switches are provided to enter data concerning the time, date, BTU, or heating value of a standard or a calibration gas to be used, high and low BTU limit (which are used in association with the metering system described below), etc. The function of the thumb wheel switches 300, including input and outlet are multiplexeo in time in a well known manner. As shown in FIGURE 9B, a CMC 68/15 interfaces with the display board P'' which is part of the display system 76 and through a printer interface 301 with a printer 80. A printer power supply is shown at 302. A stepper motor drive board 303 is provided to interface with the CNC 68/15 and to provide the control and modulation for this stepper motor 61 or 140. The CMC 68/15 includes conventional components contained in a conventional, commercially available electronic unit and is available from RCI/Data Corporation of Sattle Brook, New Jersey. The components include a microprocessor, a memory which includes a random access memory portion (RAM), and an electrically programmed read only memory portion (EPROM), a parallel interface unit, timer, and display unit driver P''. These units are respectively connected by address buses and data buses in a conventional pre-assembled board. A serial interface and 1 MHz crystal oscillator clock are also provided. The components utilized in one CMC 68/15 used in one embodiment were standard off-the-shelf items and the are listed below as follows: - Microprocessor 201 MC68GG Memory 202 2114 RAM lKx4 2716 EPROM 2Kx8 Parallel Interface 203 MC 6821 Timer 204 MC6840 Display Driver 205 Litronics DL 1650 Serial Interface 214 2651 Signetics 4MHz Crystal Oscillator Knight Individual components available from various manufacturers such as Motorola, Texas Instruments, etc. FIGURE 9C depicts the details of the flame safeguard and gas safety system which may be used with the present invention. In addition to the components described in relation to FIGURE 2 include solid state relays 310 and 311 and power supplies 312, 313, and 314. The customer safety shutdown may also be provided as shown by the dashed lines at 315. In operation, when the system is started, air and gas flow are initiated through the particular system utilized and the burners ignited by the spark ignition in conventional fashion. The flame safeguard units 46 and 54 then indicate the presence of a flame through the signal lines P14 and P17. The signal is debounced as explained below in conjunction with FIGURE 10. The debounced signal causes the contacts 49 and 51 to close thus allowing the gas safety valve 56 (and the safety shutdown valve if used) to remain open. The debouncing circuit is denoted by the dashed line labeled 316. The system basically includes an MC14490 debouncers which stabilizes the relay contacts of the flame safeguard device and also the inputs from the board P' concerning the calibration command and output date commando. Also shown on sheet a of FIGURE 10 are a threshold detector system indicated at 330 and circuitry associated with the one Hz interrupt clock which controls the program logic sequencing (discussed below) at 330. The signal from the ZrO2 sensor is compared to a predetermined threshold value in the threshold detector as by a comparator 321. At the point of stoichiometry, the output changes from a low signal to a high signal indicating that the point of stoichiometry has been passed going from air rich to fuel rich. As explained below, when the system is tracking properly, the indication should alternate from air rich to fuel rich, etc., to show that the system is tracking on the point of stoichiometry. The 1 Hz interrupt clock system 330 includes a counter 331 and a comparator 332. The comparator 332 is utilized to determine when the counter 331 has reached 0 indicating that a full second has passed and it is time to activate the interrupt. The counter is then reset and begins timing for the next sequential interrupt. Counter 331 basically rides a conventional 60 Hz power input down until it equals a 1 Hz time clock. The system indicated by the block 330 in FIGURE 10B is basically an analog-to-digital converter system which converts analog data received at various parts of the system into a form usable by the central processing unit of the system. These include high and low temperature limits for the air and gas of the system along with actual values sensed and numbers pertaining to the calibration gas and high and low BTU limit set for the operation of the system as described in greater detail below. The system includes the constant current source at 331, typical analog multiplexes at 322 and 323, and a voltage-to-frequency converter 324 which are combined in a well known manner. The output of the VFO counter is sent to a timer in the CMC 68/15 where the signal is properly multiplexed and the periods measured. It should also be mentioned in regard to FIGURE 10A that the sonalert circuit is shown at 345. The system is designed to sound an alarm when the BTU measurement is out of the limits that have been dialed in on the proper input thumb wheel switches. Circuit 345 provides the driver circuitry for this sonalert. A representative software logic control schematic layout in accordance with the present invention will now be described in accordance with FIGURES 11-17. FIGURE 11 depicts a layout of the basic routines shown in greater detail in FIGURES 12-17. They include a main routine 400 with initialize subroutine 401, startup task 402, calibration task 403, data logger task 404, display task 405 with associated time and date check 406, search task 407, display task 407, read temperature task 408. Other associated subroutine are shown at 409, 410 and 411. The main routine, of course, controls the interaction of the various tasks. A. particular system described in relation to FIGURES 11-15 involves a system utilizing preferred rotary valve system as depicted in FIGURE 2. FIGURE 12 depicts the logic diagram for the main routine in accordance with the preferred embodiment. As with all such systems, operation cannot begin until the entire system is activated or initialized as at 401. Upon power of the instrument, then, the first step in the software logic is to call the initialize subroutine which enters at 420 in FIGURE l2B. This happens as soon as the instrument is started and before the sampler vent burners are lit. The initialize subroutine then initializes the parallel interface at 421, the time module at 422, and the serial interface unit at 423. These modules are part of the 68/15 board and must be initialized and configured as predetermined in the system. Following this, the initialize subroutine exits at 424 and the main subroutine continues bv transferring control from the initialize subroutine to the startup task 402. The startup task is found in FIGURE 13. The logic flow enters at 430 and causes a startup message to be displayed on the display at 431 which tells observers the state of the instrument. The software then initializes the flame safeguard and sparking device to light the gas mixtures at both burners. During startup, the stepper motor is modulated by the frequency of the output of the timer model 422 which was initialized during the initialize subroutine. At startup, the frequency is varied to locate a mixture of air and fuel that will sustain a flame by increasing the values of frequency in accord with a lookup table in the microprocessor EPROM memory. Thus, after the gas valves allowed to be open as at 432 and the flame safeguard device started as at 433, the index 434 is initially at 0 or the first selected frequency in the table. If the flame safeguard system indicates the presence of a flame at 435, a five-minute delay is initiated at 436 to allow the sample gas burner to stabilize and the ceramic sensor to achieve its proper operating equilibrium temperature. At that point, the logic flow exits at 437. If, on the other hand, presence of a flame is not indicated at 435, the stepper motor frequency is indexed to the next position at 438 and 439 such that the mixture is slightly enriched. A ten-second delay is implemented at 440 so that the mixture may stabilize at the burner. After this delay1 the logic flow again is routed to 435 via 441 and the sequence repeated until flame is indicated to be present or 90 seconds passes at 442 in which case the flameout message 443 is displayed and the instrument is placed in a manual lockout state at 444 which requires the attention of service personnel. Once the burner flame is stabilized and the startup logic flow exits at 437, the control returns again to the main routine which thereafter transfers control sequentially to the other tasks as controlled by the real time interrupt subroutine 409. The real time interrupt times out once every second as shown in FIGURE 10a and controls the timing of the running of each of the other tasks. That routine also keeps the date and the time current. The first of these tasks is the call search task 407 which is shown in detail in FIGURE 14. Thus, when the real time interrupt indicates that the search task should be called, the logic flow enters on 450 and the search task is begun. It is the search task that attempts to find the point of the stoichiometry mixture ratio and thereafter t6 track this ratio as closely as possible such that the sample burner mixture is maintained as close as possible to the stoichiometry point of the mixture of interest. As previously descried, the ZrO2 sensor provides a continuos feeback signal dependent upon the partial pressure of oxygen in the sample combustion chamber. This feedback signal is continuously compared to a threshold or set point in the threshold detector. Thus, the first inquiry made by the search task at 451 is whether in fact a transition has taken place, i.e. whether the ZrO2 feedback has crossed the threshold. If not, the status of the search timer is checked at 452 and if this is not timed out the logic flow exits at 453 until the next time the search task is called by the real time interrupt. If no transition has taken place but the searcr timer has timed out, this indicates by the state of the threshold indicator that the mixture is either on the ricr or lean side of the threshold or transition point and therefore a change in the ratio is indicated if it is to approach the stoichiometric or transition point. This is accomplished by first incrementing a no transition counter 454 which indicates that no transition has taken place for a given number of counts. If that given number is greater than 2 as at 455, the value of delta is checked. Delta is equal to a given amount related to the amount by which the frequency of the stepping motor is changed to speed uF or slow down and thereby change the air-fuel ratio at the sam- ple burner. The maximum delta is given 2 value of 12'. Thus, if the no transition counter has a value greater than 2 and the value of delta at 456 is equal to 125 which is the maximum, the signal goes via 457 to 458 where a determination as to whether the mixture is air rich or not depending on the state of the threshold detector is made. If, howev- er, delta does not equal the maximum of 128 at 456, delta is doubled at 459 and the increment no transition counter 454 is cleared at 460 and the logic flow proceeds to 458. If the no transition counter has not yet reached a value greater than 2, the logic flow also proceeds to 458. After the decision at 458, the stepper time is either increases or decreased by the amount delta 461 and 462, respectively, depending on whether the mixture is determined to be air rich or not. Of course, by slowing down the stepper tire, the frequency of steps is decreased and the speed of rotation of the rotor is decreased thereby leaning the mixture. Thus, if the decision at 458 was that the mixture was fuel rich, the stepper time is increased by the amount delta thus slowing down the rotation by a given related amount. The stepper frequency is then compared with a maximum stepper time or slower rotor speed of 3300 microseconds. If the speed is greater than this at 464, it is reset to 3300 microseconds and the search task outputs a new frequency 465 and 466 exiting at 467. Likewise, if the mixture is determined to be air rich, the stepper timer is compared at 468 which its slowest allowable speed and reset if nezess at 469 with the output again bei?ng modulated at 465 am 466. In similar fashion, if the search te@@ @@rst indicates that in fact a transition has occurred, tner. the no transition counter 455 is cleared at 470 and the value of delta checked at 471. If delta is greater than 1, which is the minimum delta, then the inverse of the reaction at 459 occurs and the value of delta is halved at 47 with the logic flow then proceeding to 458 where the same sequence just described occurs. The value of delta may vary from 1 to 128 and the purpose of doubling and halving delta is required is to attempt to speed the search operation in an effort to bracket the transition point such that close tracking of the stoichiometric air-fuel ratio can be accomplished. As can be seen from the search task of FIGURE 14, if delta cotin- ally equals 1 and a transition takes place upon each search, a very low modulation about the stoichiometric point occurs and the system is truly tracking correctly, assuming that the mixture itself does not change. The search task is normally called about every two seconds which gives some delay time for the ZrO2 sensor to stabilize after each change. After the search task logic flow exits at 467, control is returned to the main routine as interfaced by the real time interrupt. The rest of the main routine is concerned with a series of other tasks which are interfec?d with the main routine by timers, which, upon timing out, enable the other tasks to gain control and be executed. In this manner, if the calibration timer is eqJa to û when the logic flow is sequenced at 480, the C2 ibr- tion task 403 will be called. Other such timers include data logger timer 481, display timer 482, read temperature timer 483, and two panel initiated buttons including a call- brate button and a print button 484 and 485, respectively. Assuming that the calibration timer is timed out, or that the push button 484 has been pushed, the main routine relinquishes control to the calibration task of FIGURE 15. In this task, the logic flow enters as at 500 and selects the calibration gas at 501. This causes the three-way inlet valve to switch from sample gas or gas of interest to calibration gas as the fuel gas. After a 30-second delay to allow the burner to stabilize at 502, t.t system is checked as to whether it is tracking at 503 prior to search routine 407. If not, this is checked continually on a one-second delay as at 504 until tracking occurs at which time the read temperature task 408 (discussed below) is called. Based on the output of the read temperature tass 408, the constant K1 utilized in the BTU calculation as described is recalculated utilizing any necessary terpera- ture correction as at 505 and the inlet valve is again switched back to the sample or unknown gas of interest as at 506 and the logic flow exits at 507 returning control back to the main task. The method of correction for terrerature is discussed below in relation to the read temperature tas < in FIGURE 17. The caiibLai-or, t,.,er i reload'cud at 487 ad calibration will not occur automatically until the calibration timer again times out. The calibration timers is normally set for a period of up to 12 hours such that if calibration is successful, it occurs only rarely in the operation of a device. When the data logger timer 431 times out, the data logger task 404 is called to cause the data at 487 to be printed and thereafter the data logger timer is reloaded at 488. This routine allows certain data to be periodically printed to monitor the operation of the system. In a like manner, the display task 405 is called and, as seen in FIGURE 16, logic flow enters at 510 and asr. the status of the time and date thumb wheels as at 511. Thus, the display can update the time and date as at 513 and 514, calculate the BTU or heating value of the fuel from tne floating point mathematics as at 515, and display the results as at 516. Returning to the main routine, again the display timer is reloaded as at 489. In a like manner, the main task executes the read temperature task 408. This task is shown in detail in FIGURE 17. The logic flow enters at 520, and the input from the calibration resistor which is the standard against which the temperature sensor is compared is called at 521. The voltage-to-frequency routine is called at 522 which outputs a frequency signal based on the calibration resistor. In a similar manner, at 52if,26, frequency signals are generated for the air temperature sensor and the mixture temperature sensor and from these at 527 and 528 the resistance of the air sensor and mixture sensor can be calculated and the air and mixture temperature is derived at 529 and 530. After completing one cycle of the main routine, the routine is returned to being timing through the tasks again as at 490. Thus, the routine begins all over again and continues to continually go through the various rout:ri as determined by the real time interrupt and the various timers associated with each routine. The mechanical components of the systers of FIGURES 2 and 3 may be any conventional components which meet the requirements of the system. These include the pressure regulators, temperature sensors, flame safeguards, safety and ignition systems, and burners. These are all conventional items available from a variety of manufacturers. In the embodiment of FIGURE 2, the stepping motor used in one successful embodiment was a 6000 series SLO-SYN steFF1 motor available from the Superior Electric Company of Bristol, Connecticut. These motors have a 1.8 step angl or a total of 200 steps per revolution of the shaft. Thus, each control input can step the motor as little as 1.E-. The flexible coupling 105 used in one successful embodiment in conjunction with the stepping motor was an MCA 100 HELI-CAL flexible coupling manufactured by the HELICAL Products Company, Inc. of Santa Maria, California. It can readily be seen from the above description that the several proportioning systems which have been described in accordance with the heat content measuring sys tem of the present invention may have many applications elsewhere. These proportioning systems have characteristics that make them guite useful for the accurate mixing of all types of gases and even liquids in association with other systems. As can be seen from the above description, the heat content measuring system of the present inventIon including the several alternate proportioning systems provides an effective, simple, and accurate system for determining the heat content of gaseous hydrocarbon fuels. Results utilizing the invention i-ndicate that very high accuracies can be obtained readily.

Claims: Claims: 1. A method of determining the heating value of gaseous fuels1 c h a r a c t e r i z e d b y the steps of: establishing a mixture of fuel and air of known proportions; combusting said mixture of known proportions; sensing the presence or absence of oxygen in the products of combustion of said mixture with a solid state electrochemical sensor; adjusting the proportions of fuel and air in said mixture based on the output of said sensor until said mixture is substantially stoichiometric; determining the heating value of said fuel substantially at said stoichiometric point from a known relationship between the heating value of the fuel constituents and the amount of oxygen required for stoichiometric com bustion thereof. 2. An apparatus for determining the heating value of gaseous fuels1 c h a r a c t e r i z e d b y, a) a mixing device (60) for establishing a mixture of a gaseous fuel, the hecc content of which is sought to be determined, and aiPanown volumetric proportions; b) a burner (44) for the combustion of said mixture of known proportions; c) a sensor(48) for sensing the presence of combustibles or oxygen in the products of combustion of said mixture, said sensor providing an output signal quantitatively indicative of said combustibles or oxygen in said products of combustion; ; d) means (70, 611 60) for adjusting the proportions of fuel and air in said mixture in response to the output of said sensing means until said sensor means indicates that said mixture of known pro portions is substantially stoichiometric; e) a calculator (70) for determining the heating value of said fuel from a known relationship between the heating value of the fuel constituents and the amount required for stoichiometric com bustion thereof. 3. An apparatus for establishing a mixture of known volumetric proportions, in particular for mixing fuel gas and air in an apparatus according to claim 2 c h a r a c t e r i z e d b y, a rotary pro portioning system (60) comprising at least: f) a first inlet (62) adapted to connect to a source of a first component (gas) to be mixed; g) a second inlet (63) adapted to connect to a source of a second component (air) to be mixed; h) a first outlet i65ì lor diuiiryiny al, tLrluent mixture; i) a sensor outlet (64) for discharging the component mixture of interest; ; j) a rotable member (100), which is provided with a plurality of fixed hollow volumes (122) having open accesses at the extremes thereof such that upon rotation of said rotatable member each of said volumes is sequentially connected between said first inlet (62) and said first outlet (65) and said second inlet (63) and said second outlet (64); k) a motor (61) for rotating said rotatable member (100). (Fig. 4+5) 4. An apparatus of claim 3 wherein the number of inlets (62163) equals the number of components to be mixed. 5. An apparatus of claim 3 or 4, c h a r a c t e r i z e d i n t h a t the motor (61) is a stepping motor. 6. An apparatus of claim 3,4 or 5, c h a r a c t e r i z e d b y a controller (70) for controlling and varying the speed of said motor (61). 7. An apparatus according to one of claims 3 to 6 characterized by 1) said rotatable member (100) comprising a cyl inder (100) provided with a series of spaced cylindrical holes (122) therethrough extending in axial direction and distributed around the circumference of said cylinder m) said first inlet (62) comprising a stationary partial annular first inlet slot (119) juxtaposed to and connecting the inlet accesses (124) of the holes ('.22) in said rotatable member located opposite said slot; n) said second inlet (63) comprising a stationary second inlet slot (118) spaced from said first slot (119)-said second slot also being juxtaposed to and connected to the inlet accesses (174) of said holes (122) in said rotatable member located opposite said second slot (118); ; o) said outlet (64,65) comprising stationary counterpart outlet slots (121,120) symmetri cal to and aligned with said first and second inlet slots (119,118), said outlet slots being juxtaposed to and connecting with the outlet accesses (123) of said holes (122) in said rotatable member (100); p) said first and second inlet slots (119,118) respectively being connected with said source of said first and said second components to be mixed; and q) said first outlet slot (121) being connected to an effluent and said second outlet slot (120) containing the mixture of interest. 8. An apparatus of claim 7 c h a r a c t e r i z e d i n t h a t said first (119,1211 and second (118,120) slots are of different lengths. 9. An apparatus according to one of claims 3 to 6 characterized by r) said rotatable member comprises a cylinder (144) provided with dual inner and outer series of spaced holes (164) extending in axial direction and distributed around the circumference of said cylinder and forming a symmetrical pattern such that each inner hole is paired with a correspondung outer hole,and recesses (165) connecting the bottoms of the holes in each pair forming U-tubes thereby; S) inner (148, 150) and outer (147,149) pairs of parallel fixed partial annular slots (147 to 150) juxtaposed to and aligned with said inner and outer series of holes (164), each of said pairs of slots comprising a shorter (149,150) and a longer slot (147,148) spaced apart and wherein the two shorter and two longer slots are in radial alignment; ; t) one (149) of said shorter slots (149, 150) connects to said source of said first component (gas) to be mixed and the other (150) of said shorter slots connects to an effluent outlet (65); and u) one of said longer slots (147,148) connects to said source of said second component (air) to be mixed and the other of said longer -slots provides an outlet (64) for said mixture of interest (Fig. 6+7) 10. An apparatus according to claim 7,8 or 9 characterized in that said inlet connections (62,63) to said sources of first and second components and said outlet connections (65,64) to effluent and said mix ture comprise openings (127 to 13Oil55 to 159) connecting said slots (118 to 121; 147 to 150) and wherein the corresponding openings connecting said inlet slots and said outlet slots are lo cated at opposite extremes of said slots such that the contents of the slots also tends to flow along said slots in traversing the system. 11. An apparatus according to one of claims 7 to 10 c h a r a c t e r i z e d i n t h a t the disposition of said inlet and outlet openings (127 to 130; 155 to 159) accessing said slots (118 to 121; 147 to 150) relative to the di rection of rotation of said rotatable member (100, 144)is such that the first component (gas) tends to flow along the inlet slot in a direc tion opposite to the rotation of the rotatable member and the second component (air) flow tends to be in the same direction as the rotation of the rotatable member. 12. An apparatus for establishing a mixture of known volumetric proportions in particular for mixing fuel gas and air in an apparatus according to claim 2, c h a r a c t e r i z e d by I) a plurality of valves (213to 216) assembled in at leat two ordered pairs (213,214; 215,216) each pair having a first !;3,L7) and a second valve (214,216); II)a chamber (217,218) of known volume separa ting the valves in each pair; III)a first conduit (219) for supplying a first component (gas) to be mixed to an inlet port of each of said first valves (213,215) IV) a second conduit (212) for supplying a second component (air) to an inlet port of each of said first valves (213, 215); V) third conduits (226, 227) for connecting an exit port of each of said second valves (214,216) to an effluent device (223, 228); ; VI) fourth conduits (221,223) connecting an exit port of each of said second valves (214,216) to the desired location (229) for the mixture of interest; VII) valve actuator control means for alter nately positioning said ports of said valves between two positions such that in a first position said first component to be mixed is caused to flow through the first ordered pair (213,214) into said effluent (223,228) and said other component to be mixed is caused to flow through said second ordered pair (215,216) into said desired location (229) for and said mixture in a second position where in said first component to be mixed is caused to flow through said second ordered pair (215,216) to said effluent (223, 228) and said other component to be mixed is caused to flow through said first ordered pair (213, 214) to said desired location (229). 13. An apparatus of claim 12, c h a r a c t e r i z e d b y additional pairs of valves corresponding to additional components to be mixed. 14. An apparatus of claim 12 or 13, c h a r a c t e r i z e d b y a mixing chamber (222) between said valves (214,216) and said desired location (229). 15. An apparatus of claim 12, 13 or 14, characterized in that said valves (213 to 216)are poppet valves. 16. An apparatus of one of claims 2 to 15 c h a r a c t e r i z e d b y said sensor (48) comprising a substantially solid state electrochemical cell. 17. The apparaturs of claim 16, c h a r a c t e r i z e d b y a sensor cell the output signal of which undergoes a step change as the amount of oxygen sensed approaches zero. 18. An apparatus of claim 16 or 17, c h a r a c t e r i z e d i n t h a t the electrochemical cell is made substantially of -ZrO2 stabilized by a compound substantially consisLijig of hole or rrO of the rollowing, CaO, MgO, and Y203. 19. An apparaturs of claim 18, c h a r a c t e r i z e d i n t h a t said stabilizing compound consists substantially of CaO. 20. An apparatus of one of claims2 to 19, c h a r a c t e r i z e d b y regulators (32,42) for the flow of fuel gas and air entering the system; 21. An apparatus of one of claims 2 to 20 c h a r a c t e r i z e d b y cali bration means (35-37; 206-208) for cali brating said known relationship between said heating value and said stoichiometric amount of oxygen.

Inventors: KUDE, WILLIAM B., PEARMAN, A NOEL J., YOUNGBAUER, DANIEL L.
Applicants: HONEYWELL INC.
Application year: 1980
Main classification: G01N25
IPC codes: G01N33, G01N25, F23N5