US 2839892 A
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June 24, 1958 H. RosENTH-AL'. 2,839,892
GAs TURBINE oycLE EMPLOYING SECONDARY FUEL As A COOLA'NT, AND UTILIZING THE TURBINE EXHAUST GASES IN CHEMICAL REACTIONS Original Filed Oct. 4, 1947 United States Patenti' ffice GAS TURBINE CYCLE EMPLOYING SECONDARY FUELVAS A COOLANT, `AND UTILIZING THE TURBINE EXHAUST GASES 1N CHEMICAL RE- ACTIONS l Henry Rosenthal, Yonkers',
Original application October 4, 1947, Serial No. 778,001, now Patent No. 2,660,032, dated November 24, 19S 3. Divided and this application August 31, 1953, Serial No. 377 ,292l
is anims. (ci. sol-39.05)
My invention relates V to improvements in gas turbine l 2,839,892 .Patented June .24, 1958 l ofthe hydrocarbon fuel.` Inthismanner, saturated hyj drocarbons of the parafiine series may be converted into olenes and di-oleiines. This reaction is favored by the use of boron fluoride asagaseous catalyst. It will be noted that at thetemperatures utilized in Ymy turbine cycles and more particularly to gasv turbine cycles in which valuable chemical by-products maybe recovere'dfrom 'the exit gases of the turbine. lThis is a division of my Patent 2,660,032, issued November 24, 1953.
Due tothe present state Lof the metallurgical art, the temperature of the gases entering gas turbines, 'as now operated, must be limited to the maximum temperature that can .be safely handledwith .thernetals as now used in'the turbine construction. .This temperature` is now controlled by burningthe heating lfuel 'with a portion of thev total air admittedt'o the combustion ,chamber and admitting suicient secondary air to reduce the teniperature of the productsof combustionto thaty which can be safely utilized by the turbine. yThis temperature is from l000 F. to about 2000 ;Fdepending`up'on the turbine construction. A I have discovered that the 'temperatureof'the turbine can be controlled bythe addition or excess fuel orlb'y some heat absorbing reaction,'f instead of by the addition of excess air, and'that when thel temperature is sov controlled, valuable oxidation products may be recovered from the turbine exhaust.` Moreover, the yield ofv such by-products is greater than'can be obtained by other methods of direct oxidation, so far as I am aware. This may be explained by the rapidity with which the combustion products are cooled by adiabatic expansion in *the turbine, particularly if a turbine of the impulse type is used. However, my invention i's'ap'plicable both to the impulse and reaction type turbines, as either type will give quicker cooling throughout the mass of the gaseous products than obtained by other procedures. In the1impulse turbine, this cooling will be from 1/10 to 1/2 millisecond, and in a reaction turbine, it will be from 1 toll milli-seconds. (This compares to approximately 20 to 100 nulli-seconds inthe usual internal combustion engine.) This quick cooling acts to prevent the oxidation of vhydrocarbons of a type resulting principally in the formation of carbon monoxide, carbon dioxide, and Water vapor. Instead, the intermediate products of combustion can be retained, and, depending'on the' temperatures,l the contact time, the fuel used, the relative quantity loi-fuel to air, the operating pressure, and onrthe catalysts selected in the combustion chamber, various productscan be manufactured and can be recovered from the exhaust gases. 'Some of the products that can be thus obtained are alcohols, esters, aldehydes, ketones, vacid Vanhydrides, organic acids, carbon black, etc. Also, if relatively heavy hydrocarbons, such as straw oil or gas oil, are used as fuel, the cycle can be operated to crack the excess fuel used for temperature control, andihigh vgrade motor: fuel can be recovered from the turbine exhaust. The cycle is also applicable to the dehydrogenationof paratlines.
The oxidizing agent may be air, oxygen-enriched air, or substantially pure oxygen. Which of these is used will depend upon the particular circumstances, the materialv to be oxidized, and the reaction products desired. Also,
cycle, the boron lluoride will ynotube `unduly corrosive, but care mustbe takento prevent corrosionfafter ,the gases have .left the turbine andthe temperature is reduced, y Other gaseous catalysts may be usedA with my cycle, depending'upon ythe Idesired ,end product. Thus, nitric oxide (NO),V nitrogen tri-oxide (N203) and nitrogen tetra;
oxide (N294) may be usedto catalyze oxidation reactions.
It willbe noted that some of these materials will be formed'in the high temperature zone of combustion, through `the interaction Vof the nitrogen and the oxygen A of fthe air, when air', is Vused asthe oxidizing medium.
Some of these products will persist throughout the turbine, and nappreciable quantitiesfwill remain Where the time from vthe/primaryl combustion zone to the turbineienl trance is short, thus preventing reversion of the oxides to oxygen and nitrogen before; the quick cooling:.inI the turbine acts to deter the reversion; r y
`vOther gaseous catalysts lare hydrouoric acid, and formaldehyde. The latter acts to, speed -the oxidation of aliphatic hydrocarbons into intermediate oxidation products. f f
The objects of my invention are thus, in a gas turbine cycle tov (l) Obtain higher over-all rthermal efficiency than 'is obtained in a usual air cycle, Awhichconsists essentially of ani adiabatic compressiom, anjisopiestic compression, an `adiabatic expansion, and an isopiestic expansion and in-'wliiclithe temperature attained in the isopiestic compression lis controlled byfadmission .of excess lair.
(2)7 Produce useful products vof reaction 'othervthan those of complete combustion together withthey generation ofy power.
(3) Produce synthetic chemicals as a .by-product of'A power generation. Other-objects will be apparent froml Y this specification. Y
f Prafne hydrocarbons, either straight or branchedchain, olefine's, benzene, toluene, xylene, andv other hy! drocarbons may beused as the material to be oxidized, dependingupon the'desired products. p i 1 The reaction of'paraiiin hydrocarbons to produce aldehydes ltypified by "the following reactions:
terial ,tobe oxidized is gaseous, some portion of the'v exhaust must be vented from the system in order to prevent an excess build-up lof nitrogen in the system. The. gases so vented will be suitable vfor use in-iiring boilersand for other purposes. The use of oxygen-enriched air will reduce the amountof venting required, and the 'A substantiallypure oxygen will materially Yreduce i i w( the need for venting. f
If the hydrocarbon oxidized contains three or more carbon atoms and if the operating temperaturesareheld within 'such'- limitssovtha't the amountofvcraclring to gaseous products islirnited with relation. to the :amount of' material oxidized, the fuel VVin the j exhaust' may be readily separated from the nitrogen Vby known methods whenair or oxygenenriched air is used as the'oxidizing medium.v` The nitrogen 4could be recovered and further puriedfor otherchernical uses, such as the manufacture of'` ammonia, if desired. However, the use ofjsub stantially. pure oxygen has certain advantages inthe turbine cycle as will be explained. e V"When air. or oxygen-enriched air is used as the oxidizingagent, materials rnust be compressed to the inietpressure of the turbine. Thework required for this compression utilizes an ,appreciable portion of ythe work generatedin the turbine. If substantially pure oxygen, injt'he liquid state, is used 'for oxidation, the required pressurescan be generated without gaseous compression.' Thisis particularly advantageous where thel higher hy'l drocarhons are oxidized, Aas these can be brought'up to or in;some'ca ses, by application of heat tothe liquid, thus' entirelyeliininating the necessity for gaseous' compression." Unleithisv condition the gross energy delivered from the turbineis substantially the net energy ofthe Y .The above factors will enter into the cycle when producing 'other materials than aldehydes, as described above,a s for instance, intheproduction of alcohol, ac-
cording lto the following equations:
Thereactions take placev at temperatures in excess of 750 YF.; and are favoredby the use of high pressures. This wouldV require thefuse' of compression v,in stages where gaseous fuel isV used in combination with air. However, if the fuel vhas three or more carbon atoms, and oxygen, initially liquid, is used to support the combusti'on, any pressure required as favorable to the production of the alcohols, can readily be obtained without the necessity of gaseous compression, which, as has been'explained, results in greater net energy output frontl t l1e -turbine cycle. The alcohol reactions are favored, not only by high pressures, `but also by the presence of catalysts, including 'alum' um oxides, chromates and certain other oxides, and some metals. The production of ethers, 1ikethe production of` alcohols, is favored 4by high pressures.r 4The following: reactions typify thewcycle when ethers are the desired by-product:
The production of carbon black in the'turbine cycle,V
perature is carried out at plus 1800 F., the carbon black reaction may be brought practically to completion in ac" cordance the following reactions:
C3H 3C|4H2 Similar reactions occur if hydrocarbons of higher molecular weight are used in the cycle. The use of methane leads to the production of a reinforcing type of carbon black. The use of the higher hydrocarbons leads to the production of a soft type of carbon black. In order to provide heat for the above reactions, an oxidation as illustrated by the following equations, takes place substantially simultaneously with the reactions leading to the formation ofl carbon.
Similar reactions occur used as fuel.
At lower temperatures than are desirable for carbon formation, vheavy petroleums c'an be introduced into the combustion'chamber of my turbinecycle, preferably as a'ne spray, a'iidlighter liquid hydrocarbons, such as gasoline, 'will b'formed. An inlet temperature of 750 ther-required pressure by pumping them in a Hquidphase F. to 110()ov F. at vthe turbine inlet is conducive to this reaction. Like` the'reac'tion for carbon formation, a portion of the fuel is combined with oxygen to supply the heat energy. Also, a single stage compressor may be used for compression, if air is used as the oxidizing medium. In' order to hold the lower temperatures desired,
a larger weight ratio ofA fuel to air is required for usual hydrocarbons'cracking than is required for ca rbon black formation.A Unlike the` cracking to carbon black, this reaction does not go to completion, so that recovery and recycling of the unreacted fuel will be required when my cycle is operated withA heavy hydrocarbon fuel for the recovery of motor fuel. Various catalysts known in theart may be used, depending upon the characteristics thatare'desired in the motor fuel recovered.
`.It vwill be understood that simultaneously with reactions similar tol Equations 1 to 11 inclusive, reactions similar to 15 and 16 may take place in or near the zone of prmaryoxidation prior to the addition of the excess combustible. This will result in secondary reactions in the secondary vzone which may be exemplified as follows:
and synthesis f hydrocarbons may be promoted. The principal reaction maybe predetermined by proper selection of the temperature, time in the primary and secondary reaction zones, relative vamounts of oxygen and oxidzable substances, and presence of some particular catalyst'. i It will further be vunderstood that the above examples are illustrative only, as under proper conditions, the reactions can be carried out to result in other oxidation products, depending on the factors cited in the preceding paragraphs and `upon the Vcharacter of the oxidizable substance utilized. Also, some lesser amounts of other oxidation products in addition to the main product desired, will be obtained simultaneously with the main reactions, except in such instances as the substances may be reacted to substantial completion in a single cycle, as for instance, the reaction tocarbon black. YThis will not appreciably alfect the value of my process, as these products will have commercial value, and in most instances, they may be readily separated from the main desired product.
,In certain instances, itmay be desirable to supply more nS than one fuel (hydrocarbon)` to the` system. Suchga con-l dition'would occur under the following circumstances: Q (a) when heavy hydrocarbons-areV introduced for cracking to motor fuels as previously described. Here, the furnace fuel is itself a mixture of various chemical sub# stances which may include recycled products.
(b) when it is desired to obtain'a vspecific chemical through the oxidation and interaction of two substantially pure'hydrocarbons, as for example in the formation of a mixed ether. r y
(c) when a specified product requires the use of a relatively expensivefhydrocarbon for its formation and it is desired to limit the use of this relatively expensive material in so far as is possible.
As an example of the latter condition, methene may be reacted with oxygen in -accordance withEquations l and 16 and vapors of naphthalene may be separately introduced into the furnace as a coolant for the reaction products of the methane combustion. If the proper conditions are maintained in the furnace, the naphthalene may be converted into phthalic anhydride by reactions whichinclude those shown by the following equations:
In a further modification of my cycle, the fuel may be reacted with oxygen in the primary zone of the furnace and the temperature of the products of combustion may be lowered by the introduction of steam or a water spray in the secondary zone in the furnace along with additional fuel. In the primary zone, the reactions are typified by (1'5) CH4+OT CO+H2+H20 (16) CHM-202 0024-211120 In the secondary zone the reactions may be typified by the following equations: v
(25) CHHFHZOcarat-1244120Coi-3H2 (26) CH4+Co2-c+2H2+Co2- .9130+2112 (27) CHrl-Z'Hao Cori-4112 Equations 25, 26, and 27 are favored by temperaturesy in excess of l500 F. and Equations 25 and 27 are further favored by the presence of excess steam. These three equations represent endothermic reactions which assist in cooling the products of Equations l5 and 16 from the high temperatures attained from those latter reactions to the temperature required at the turbine inlet. In the passage through the turbine, these gases are so quickly cooled by the adiabatic expansion, as to prevent exother'mic reversion of the carbon monoxide and hydrogen to carbon and Water or to carbon and carbon dioxide. However', the temperature of the gases leaving the turbine is suiciently high to promote the FischerTropsch synthesis in the presence of a suitable catalyst. This latter reaction may be typified by the following equations:
delivered vtothe system and fed to the combustion'chamber as a. vapor or spray, as inthis' case the gross'power from the turbine 'is substantially i the net `power of the cycle. This is due to the Vfact that the lcompressor is eliminated. t n v The hot products leaving the turbine exhaust maybe brought into heat exchange with'the relatively'cool lrnaterials entering the combustion chamber, and a gainin thermal efficiency of the cycle will result. Heating of the material to the combustion chamber by heat exchange with the hot' exhaust gases is particularly-desirable where liquid materials are used las fuel andare deliveredto the combustion chamber either asa spray or a'vapor.- Where the gases leave the turbine? ata temperature'of fromf950 F. to l350 F., Yhydrocarbonsmaylbeintroduced into the stream. Theintroduction of hydrocarbons having a molecular weight above 44, into the stream at these temperatures, will lead to theircracking..r Relatively light hydrocarbons, such as` butane, may be introduced as a'vapor and heavy hydrocarbons such'as straw-oil may be introduced as a spray. i 1
My invention may best be described by reference Ltothe following drawings, in which Y Fig. l illustrates diagrammatically, my invention as applied to the productionof formaldehyde# 4 Fig. 2 similarly illustratesrny invention as applied to the formationfof carbon black. n' "i f Fig. 3 diagrammatically illustrates my inventionas applied to the production of motor fuel thru the synthesis from carbon monoxide and hydrogen. Y v 4 It will be recognized thatthese examples are-merely illustrative of my invention, as slightly different diagrams may be desirable for the production of other products than formaldehyde, carbon black, or motor fuel. YAlso for the production of formaldehyde or carbon' black, modifications may be made in the details lof the cycles illustrated, without departing from the spirit of my invention. This will be readily understood by'on'e skilled in the art. l v 't Referring to'Figure l: the air compressor 1, andthe methane compressor 2 are mechanically connectedfto' each other and to gas turbine'3 .and the electric generator (or other load) 4 by means of the shaft 7. The gas turbine 3 is preferably an impulse typefturbine. Air from the atmosphere entersv thetcompressor 1 by means of pipe 3, and the compressed air -from the compressor 1 is delivered by pipe`9 to the primary `reaction chamber 6 of the furnace 5,'thru enlarged portion' 10and pipe 9. Methane is delivered zto the compressor 2 by means of the pipe 11 simultaneously with return gas'by means of the pipe 22, as will be explained later.' 'The compressed gas is delivered tothe primary lreaction chamber 6 of the furnace 5 by means' of pipes I2 and 13, and to the secondary reaction chamber 26 of' the-"furnaceV 5 by means of pipes 12 and 14. The enlarged portion 10 of pipe 9 permits the pipe 13 to be p lacedwithinhe stream of incoming air so that Ythe combustible is sur` rounded by air as thevtwo are delivered tothe primary reaction chamber. Gas from the secondary chamber 26 may also enter the primary chamber 6 by the ports 15 in the partition V27 vseparating the `secondary chamber from the primary chamber. The partition 27 y and the furnace 5 are preferably made of chromium upon which a layer of oxide has been built up to assistgin ythe conversion to formaldehyde. primary chamber is adjusted to maintain continuousignition of the methane. n The quantity of methane addedin the secondary chamber is adjusted to reduce ythe tem.
perature of the combustion products entering the turbine to the desired amount and to promote the desired reaction. The heated gas, after reaction, is led,t`o the turbine 3 by means of the pipe 16. In the turbine, the gas is expanded while doing work, which effectively :reduces the temperature to an amount which substantially prevents further chemical reactions in theg'as stream. The ex-A panded gas is ledfrom'the turbine S'by' the pipe 417"tok The ratio ofl gas toair in the` fi? the recovery system 18 which, in this instance is shown as ,a countercurrent scrubber, to whichcold water or other absorbent is; introduced thru the pipe 24 and the solution of formaldehyde s removed by the pipe 25 to` any suitable formof concentration system (not shown). The scrubbed. gas, substantially free from formaldehyde, is withdrawn ,from the scrubber 18 by the pipes 19 and 20 tothe gas holder 21, from which it may be withdrawn by pipes 20 and vZ2 and returned to thecompressor 2 or by pipe23by which it is withdrawn from thesystem. To prevent'an'excessive buildup of nitrogen which is introduced into the system in air thru pipe 8, somewithdrawal must be made ofthe reacted gases thru Vpipe 23. If there are other uses for heating gas, all of the gas rejected byr the scrubber 18 may be withdrawn from the system by the pipe 23. In this instance, no methane would be delivered tofthe compressor 2 by the pipe 22, andthe entire supply of methane would be delivered to the system by the pipe 11. The following example is based upon the latter operation as computed for possible yields:
Temperature of air to compressor 60 F.=520 R. Temperature of methanerto 4crompres- Y sor V 607 F.=520 R. Pressure at compressor inlet 15 p. Vs. i.-abs. Pressure at compressoroutlet 90 p. s. i.-abs. Temperature of gasentering turbine 1500 F =1960 R. Temperature of gas leaving nozzle 825 F Temperature.. of gas leaving turbine 1025 F =1485 R. Pounds methane consumed as fuel per pound methane to the system Pounds of air per pound methane to u system Pounds formaldehyde per pound total methane to system Pounds formaldehyde per day per 1000 kw. output ofturbine Total methane per dayk per 1000 kw. voutput (cu. ft.) Consumed methane penday (asfuel) per 1000 kw. (cu.V ft.) ouput Heating value of gas ,from scrubber (cu. ft.) Efficiency of turbine cycle, based on heat of combustion of entering methane; less heat of combustion ofvexhaust products Etlciency of air cycle turbine having same .temperature and pressure ratios :500 B. t. u. Y
The above data are based upon the use of a well-known single stage impulse turbine in which the entire adiabatic expansion takes place in a single stage nozzle placed withinV the turbine immediately following the turbine entrance.
If methyl alcohol were the des'iredproduct, a cycle similar to that shown in Fig. 1 would be applicable. However, the production of alcohol is favored by higher pressures. The scrubber 18v and holder 21 are thus operated under pressurei and the pressure of` the furnace 5 and turbine 3 is greater than when formaldehyde is the desired product. TheY ratio of methane to air is also adjusted as required.
Referring to Figure 2,`the air and gas compressors 1 and 2, turbine.3, electric generator 4, furnace 5 withl primary `reaction chamber 6 and secondary reaction chamber k26,"and shaft 7 are the same as has been explained'in connection with Fig. 1. Also, pipes 8, 9, 11, 12, 13,14, and 16 are used in the same manner` as scribed figure, 1 Pire-.1,7 leads' from .th turPine sxhaust;v to the carbon black` collecting system, which is indicated as cooler 31; and as electrostatic precipitator 28. Pipe29 is used for removing the gas exhausted from the precipitator. Injthisinstance all the gas is rejected from the cycle after theremoval of the carbon black by the precipitator. Carbon is removed from the system by the conveyor 30. In the production of carbon black, the temperature ofthe furnace is preferably held at approximately 1800" F. or in `excess thereof. No catalyst is required for this operation as the carbon produced is in itself a catalyst for the reaction to carbon. The following figures are pertinent to4 this operation, based on complete methane conversion.
Pounds of air per pound of methane 2.65 Pounds of carbon black produced per thousand cubic feet'of methane to system 23 Cu. ft. of methane per day per 1000 kw. output S300M Poundscarbon black per day per 1000 kw.
output 75,000 Exhaust gas per day per 1000 kw. output (cu. ft.) 11,700M Heating value of gas from precipitator (B. t. u./cu. ft.) 189 Efliciency of turbine cycle, based on heat of combustion of entering methane less heat of combustion of exhaust products 62.5%
Referring to Figure 3, the air and gas compressors 1 and 2, turbine 3, electric generator 4, furnace 5, with primary reaction chamber 6 and secondary reaction chamber 26, andshaft 7, are the same as has been explained in connection with Figure 1. However, the steam pipe 33 is provided in Figure 3 to furnish a source of steam to the secondary reaction chamber 26. Pipes 8, 9, 11, 12, 13, 14 and 16 are used in Figure 3 in the same manner as 4was described in connection with Figure l.
Pipe 17 leads from the turbine exhaust to the catalytic reaction chamber 34, which can be any type of conversion chamber suitable for promoting hydrocarbon synthesis reactions from CO and H2. The gas stream from the conversion chamber 34 passes by conduit 35 to the cooling and separating system 36, in which the readily condensible reaction products are removed from the stream through conduit 37. The uncondensed gases pass from the cooling and separating system by the conduit 38. These gases may be discharged from the system by conduit 39, or they may be re-circulated back to the system. Thus, they may be led into a compressor 43 by pipe 46, where they are compressed, and led by pipes 40 and 41 back'into pipe 17 where they are used to cool the gases from the turbine 3 and are re-circulated back thru reaction chamber 34.V
If compressor 43 is suitable for delivering gas at high pressure, the gases from the separating system 36 may be passed 'back to the combustion chamber by pipes 38 and 46, compressor 43 and pipes 40 and 4S. As an alternative method of controlling the temperature of the gases entering reaction chamber 34,a cooler 42 may be provided in pipe 17 for conducting gas from the turbine 3 to the reaction chamber 34.
Now, having described my process in a manner that may be readily understood by one skilled in the art, I claim:
1. A process for making valuable products of incomplete oxidation of a fluid-fuel in conjunction with the operation of a gas turbine, which includes the steps comprising, passing under superatmospheric pressure a combustible fluid to be oxidized as a stream into a primary reaction zone, confined in a reaction chamber, also under superatmospheric pressure passing an oxidant into said zone as a stream, promoting exothermic reactions of said combustible fluid with said oxidant in said zone at a high temperature, above 2000 F., v passing the hot reaction products thus made Adirectly andcontnuously from said F. but above 750 zone to a secondary reaction zone of' said chamber, immediately mixing it therein with additional reactants, including steam or water, thereby promoting chemical endothermic reaction in the mixture with the formation =of carbon monoxide and hydrogen while lowering the temperature of the reacting fluid mixture to below 2000 F. but above 750 F., passing the thus cooled reacting mixture immediately into a gas turbine and therein materially reducing the temperature of the latter mixture while simultaneously reducing its pressure, and finally passing the turbine exhaust gases, containing carbon monoxide and hydrogen into a reaction chamber in the presence of a catalyst, utilizing the sensible heat of the turbine exhaust for initiating catalytic reaction.
2. In a gas turbine cycle of a suitably connected gas turbine unit, the steps comprising passing a stream initially containing a combustible material into the primary reaction zone of the combustion chamber of said unit and substantially completely burning said material therein, thus raising the temperature of said stream above 2000I F., introducing additional combustible material and steam 'or water into a secondary reaction zone of said chamber, passing the thus heated stream from the primary reaction zone into the secondary reaction zone and mixing it with said additionalcombustible material and steam or water and mixing it therewith, thereby promoting endothermic reactions in said secondary reaction zone and lowering the temperature of the reacting mixture to below 2000 F., then substantially immediately passing the hot reacting mixture into a gas turbine and lowering its temperature by substantially immediate adiabatic expansion, whereby the hot reacting mixture is eifectively cooled, and finally passing the turbine exhaust gases, containing carbon monoxide and hydrogen into a reaction chamber in the presence of a catalyst, utilizing the sensible heat of the turbine exhaust for initiating catalytic reactions.
3. The cycle described in claim 2 in which the combustible material introduced into the secondary reaction zone is `diierent from the combustible passed into the primary reaction zone. g
4. The cycle described in claim 2 in which the steam or water is introduced into the secondary reaction zone as a separate stream from the additional combustible material.
5. In a gas turbine cycle of a suitably connected gas turbine unit, the steps comprising, passing a gaseous stream initially containing a combustible material into Vthe primary reaction zone of the combustion chamber of said unit under superatmospheric pressure, promoting substantially complete combustion of said material therein to raise the temperature of said gaseous stream to above 2000 F., introducing a second stream of combustible material together with steam or water also under superatmospherie pressure at a lower temperature than 2000 F. into a secondary reaction zone of said chamber, passing the thus heated first mentioned gaseous stream while at a temperature above about 2000 F. into the secondary reaction zone and mixing it with second stream of material therein, thereby promoting endothermic reaction, the rate of feed of, said second stream being so regulated that the temperature of the mixture is lowered below about 2000 F., then substantially immediately passing thehotj reacting gaseous mixture in the latter temperature range into the turbine of said unit and lowering its 'temperature immediately by substantially adiabatic expansion therein, and finally passing the turbine exhaust gases, containing-carbon monoxide and hydrogen, into a reaction chamber in the presence of a catalyst, utilizing the sensible heat of the `turbine exhaust for initiating catalytic reaction. Y
6. The cycle described in claim 5 in which the combustible material introduced into the secondary reaction zone is diferent from the combustible material introduced into the primary reaction zone.
7. The cycle described in claim 5 in which the steam or water is introduced into the secondary reaction zone as a separate stream from the combustible material.v
8. In a gas turbine cycle adapted for thegeneration of power 'in a suitably connected gas turbine unit in which gasiform products of incomplete oxidation are produced, the steps comprising, continuously introducing under superatmospheric pressure into the reaction zone of said unit both a stream of lfuel and a stream of gasiform uid containing oxygen in such proportion as to supply complete oxidation of said fuel, initiating and promoting oxidation in an oxidationphase, whereby at least a portion of the fuel is'completely oxidized and the temperature of the resulting reaction products is raised to above 2000" F., continuously withdrawing the gas stream of oxidized products from the oxidation phase and substantially immediately passing vsaid gaseous stream into a reduction phase with the addition of a second stream of combustible material with steam or water under superatmospheric pressure and a temperature substantially less than 2000" F., whereby the hot products from the oxidation phase are cooled and a portion of the highly oxidized products of the oxidation phase are reduced to lower oxides by reacttons with said second stream, continuously withdrawing the reacting products in a gaseous stream from the reduction phase at a temperature below 2000 F., but about 1200 F., and substantially immediately discharging said latter lstream into the turbine of said unit and substantially adiabatically expanding and cooling it therein, and finally passing the gases containing hydrogenyand carbon monoxide discharged from said turbine linto a reaction' chamber in the presence of a catalyst, utilizing the sensible heat of the turbine exhaust gases for initiating catalytic reaction.
9. The cycle described in claim 8 in which the combustible material introduced into the reducing phase' is different from the combustible material introduced 'into the oxidizing phase.
10. The cycle described in claim 8 in which the combustible material introduced into .the reduction phase is introduced separately from the steam or water.
1l. In a gas turbine cycle adapted for the generation of power in a suitably connected gas turbine unit, in which gasiform products of incomplete oxidation are produced, the steps comprising, continuously introducing under superatmospheric pressure into the primary reaction zone of the combustion chamber of said unit both a stream initially containing vapor phase fuel and a stream of gasiform fluid containing free oxygen, initiating and promoting the complete combustion `of said stream of fuel in said oxygen containing stream in said zone, the
amount of said oxygen being sufficient for the complete' combustion of said fuel', thereby raising the temperature of the combined stream considerably above 2000 F., continuously passing the hot products of the combustion while under pressure into a secondary rea-ction zone of said chamber simultaneously introducing a predetermined additional amount of said fuel in a stream under superatmospheric pressure and a temperature considerably -below that of the stream from the primary reaction zone into said secondary, reaction zone and mixing it therein with the saidv hot products of the combustion, thereby causing the latter fuel to yreact endothermically with the said products of combustion, lowering the temperature of the latter, passing the gaseous mixture while reactions are still occurring therein, into the turbine of said unit and substantially adiabatically expanding and cooling it therein, and then withdrawing the expanded gaseous products from the turbine and introducing thereto a iluid hydrocarbon having a molecular weight in excess of 44, and maintaining said hot gas stream in conta-ct with said hydrocarbon for sufficient time to promote thermal cracking for a portion of said hydrocarbon.
12. The cycle described in claim ll in which a catalyst is added to promote cracking of the final hydrocarbon addition.
13. `In a gas turbinecycle of a suitablyconnectedgas turbineunit, the steps comprising, passing ,aggaseous stream initially Vcontaining a combustible material into the primaryvreaction zone of the combustion chamber of said unit under superatmospheric pressure, promoting substantially complete combustion of said material therein to raise the temperature of said gaseousL stream above 2000,v F., introducing a second stream of combustible material also under superatmospheric.pressure ata lower temperaturethan 2000i. F. into a secondaryreaction zone of said chamber, passingthethus heated iirst mentioned gaseous stream while at a temperature above about 2000 F.. into said secondary reaction zone and mixing itwith said second streamrof combustible material therein thereby promoting endothermic reaction of the latter material in the mixture, the rateof feed of said second stream `being so regulated that the temperature of the mixture is lowered below about 2000 F. but above 7 50 F., then substantially immediately passing the hot reacting gaseous mixture in the latter temperature range into the turbine of said unit and lowering its temperature immediately by substantially adiabatic expansion therein, whereby the hot reacting mixture is effectively further cooled, and then withdrawing the expanded gaseous products from the turbine and introducing thereto a fluid hydrocarbon having a molecularrweight in excess of 44, and maintaining said hot gas stream in contact with said hydrocarbon for suicient time to promote thermal cracking of a portion of said hydrocarbon.
14. The cycle described in claim 13 in which a catalyst is added to promote cracking of the nal hydrocarbon addition. a Y
15. In a gas turbine cycle adapted forthe generation of power in a suitably` connected gas turbine. unit in which gasiform products of incomplete `oxidation are produced, the steps comprising, continuously introducing under superatmospheric pressure into the reaction zone of said unit both a stream of fuel and a stream of gasiform fluid containing oxygen in such proportion as to supply complete oxidation of said fuel, initiating and promoting oxidation in an oxidation phase, whereby at least a portion Vof the fuel is completely oxidized and the temperature `of the resulting reaction products is raised to above `2000" F., continuously withdrawing the gas stream of oxidized products from the oxidation phase and substantially immediately passing said gaseous stream into a reduction phase with the addition of a second stream of combustible material under superatmospheric pressure and a temperature substantially less than 2000 phase are cooled and a portion of the highly oxidized products of the oxidation phase are reduced to lower oxides by reactions with said second stream of combustible material, continuous withdrawing the reacting products in a gaseous stream from the reduction phase at a temperature below 2000 F. 'but above 1200 F. and substantially immediately discharging said latter stream into the turbine of said unit and substantially adiabatically expanding and cooling it therein, and then withdrawing the expanded gaseous products from the turbine and introducing thereto a Huid hydrocarbonhaving a molecular weight in excess of 44, and maintaining said hot gas stream in Contact with said hydrocarbon for suicient time to promote thermal cracking of a portion of said hydrocarbon.
16. A gas turbine cycle for the generation of power comprising the steps compressing a gasiform combustion supporting Aiiuid to increase its pressure; passing the thus compressed uid substantially continuously into a combustion chamber while simultaneously a combustible into said chamber in controlled amounts; promoting substantially complete combustion in said F., whereby the hot products from the oxidation introducing temperature below 2000 tion; substantially immediately passing the reacting gasesubstantially constant sensible heat remaining from chamber at`substantially constant pressure to raise `the temperature of the combustion products above 2000 F.; passingthe thus heated combustion products into a secondary reaction zone under substantially the same pressure and simultaneously introducing an amount ,of com,- bustible'uid in excess of that required for complete combustion, along with steam or water to reduce the temperature of the resulting stream below 2000 F. in part by endothermic reactions; immediately passing the latter stream from the. substantially constant pressure stage into an expansion stage in which latter stage the reacting gaseousvmixture is expanded with a decrease in pressure, whereby intermediate combustion products formed in the substantially constant pressure stage are quickly cooled adiabatically and finallypassng the expanded gaseous stream at substantially constant pressure into a reaction chamber in the presence of a catalyst and promoting catalytic reactions therein utilizing the sensible heat remaining from the expansion stage.
17. A gas turbine cycle for the generation of power comprising the steps, compressing a gasiform uid containing free oxygen with increase in pressure, passing the. thus compressed fluid substantially continuously vinto a combustion chamber while simultaneously introducing a hydrocarbon fuel into said chamber in controlled amounts, promoting substantially complete combustion in said chamber at substantially constant pressure to raise the temperature of the combustion products above 2000 F., passing the thus heated combustion products into Va same pressure and simultaneously introducing an amount of hydrocarbon fuel in excess of that required for complete combustion, along with steam or water to reduce the ltemperature of the resulting stream below 2000 F. in part by endothermic reactions, immediatelypassing the latter stream from the substantially constant pressure stage into an expansion stage in which latter stage the reacting gaseous mixture is expanded with a decrease in pressurey whereby the intermediate combustion products formed in the substantially constant pressure stage are quickly cooled adiabatically, and finally passing the expanded gaseous stream at substantially constant pressure into a reaction chamber in the presence of a catalyst and promoting catalytic reaction therein utilizing the vsensible heat remaining from the expansion stage.
v18. A gas turbine cycle for the generation of power comprising the steps of compressing a gasiform fluid with increase in pressure; adding an amount of heat at substantially constant pressure, said heat being added by addition of Huid fuel to said gasiform stream in an amount substantially required for complete combustion to bring the temperature of the stream in excess of 2000 F. and then adding an additional amount of fuel and an amount of steam or water in quantities to reduce the F. in part by endothermic reacous mixture from the substantially constant pressure stage into an expansion stage, in which the reacting gaseous mixture is expanded with decrease in pressure whereby the intermediate combustion products formed in the pressure stage are quicklyV cooled adiabatically and finally passing the product from the expansion stage into a substantially constant pressure stage in a reaction chamber in and promotingy catalytic reactions therein, utilizing the the expansion stage.
References Cited in the file of this patent UNITED STATES PATENTS secondary reaction zone under substantially theV the presence of a catalyst@ Rosenthal Nov. 24, 1953