Abstract:
Flue gases as generated in the combustion of a carbonaceous fuel are extracted while at a high temperature, e.g. 2000° to 3800° F, and mixed with a fuel and converted in the presence of an oxidant such as air and/or steam to a thermally generated gas stream enriched in hydrogen and/or its equivalent carbon monoxide. Conversion efficiencies based on the hydrocarbon feed in excess of 100% are achievable.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This application is a continuation-in-part of my Application Ser. No. 450,550 filed Mar. 13, 1974 now U.S. Pat. No. 4,012,488. 
    
    
     BACKGROUND OF THE INVENTION 
     In my parent application there was provided a method and apparatus to improve the recovery of fuel burning power generators and the like while minimizing emissions of sulfur and nitrogen to the atmosphere. 
     In the process as described, after combustion of a carbonaceous fuel such as coal, there is introduced a secondary hydrocarbon, such as methane, capable of forming a reducing gas into the combustion chamber to scavenge excess oxygen and create reducing atmosphere for the subsequent reduction of the oxides of sulfur to hydrogen sulfide and the oxides of nitrogen to inert nitrogen and/or ammonia with nitrogen formation being favored. 
     The gas stream is then allowed to pass through the remaining sections of the boiler and to an added catalytic conversion zone containing a catalyst capable of converting the oxides of sulfur to hydrogen sulfide by reaction with the hydrogen present in the reducing gas and the oxides of nitrogen by reaction with the reactants present to form inert nitrogen and/or ammonia at a temperature from about 300° to about 800° F. 
     Many other operations exist where there is a requirement for a reducing gas comprising hydrogen and/or carbon monoxide reductants, such as for regeneration of SO 2  absorbants, and reducing in external streams the oxides of sulfur and nitrogen. Usually such reducing gases prepared by reacting steam plus hydrocarbons at high temperatures (1200°-1800° F) over a catalyst. The principal chemical reactions which take place using methane as a typical hydrocarbon are: 
     
         CH.sub.4 + H.sub.2 0 → CO + 3H.sub.2                ( 1) 
    
     
         co + h.sub.2 o → co.sub.2 + h.sub.2                 ( 2) 
    
     another method is to burn a hydrocarbon with substoichiometric air at elevated temperatures (2000°-3700° F). The principal chemical reactions taking place in this process are: 
     
         CH.sub.4 + 1/2O.sub.2 → CO + 2H.sub.2               ( 3) 
    
     
         ch.sub.4 + 2o.sub.2 → co.sub.2 + 2h.sub.2 o         (4) 
    
     In both cases a relatively expensive hydrocarbon fuel must be used as the sole fuel and/or as the process material. In the commercial application via the steam methane reforming of (1) and (2) above, a fairly expensive furnace must be employed with high-alloy tubes to contain the catalyst and to withstand high furnace temperatures. The cost of such equipment is becoming prohibitively expensive. 
     SUMMARY OF THE INVENTION 
     According to the present invention, there is provided a more economical route to providing a reducing gas stream containing hydrogen and/or its equivalent carbon monoxide. 
     In the process of this invention high temperature gas streams generated in a reaction zone, such as the flue or combustion gases generated in furnace or present in the convection zones of the boiler, are extracted, combined with a carbon containing fuel and reacted in the presence of a quantity of an oxidant in a concentration stoichiometrically insufficient to convert all of the fuel to carbon dioxide, but sufficient to convert the carbon in the fuel to carbon monoxide. The mixture is allowed to adiabatically react to the resultant high temperature to produce a gas stream enriched in hydrogen and/or carbon monoxide. 
     In the process, the extracted gas stream is normally provided at a temperature between about 2000° F to about 3800° F. The amount of carbon containing fuel added is proportional to extracted gas temperature and will be added to provide a range from 5 to about 100 mols of carbon plus H 2  inclusive, preferably from about 15 to 50 mols per 100 mols of extracted gas. The use of high purity oxygen can permit higher than normal hydrocarbon additions by maintaining the net reaction products at a high temperature and avoiding nitrogen dilution. While conversions primarily occur thermally, a catalyst can be employed to speed the reaction, particularly especially where the extracted gas is at a temperature below about 2000° F with the normal precautions of preventing poisoning or masking of the catalyst. 
    
    
     DRAWING 
     The attached Drawing illustrates a typical embodiment of the practice of this invention. 
    
    
     DESCRIPTION 
     With reference first to the Drawing, in a power generator 10, the boiler 12 is supplied with a primary fuel normally a sulfur bearing carbonaceous fuel such as pulverized sulfur bearing coal or sulfur bearing hydrocarbon liquid in line 14 along with preheated air from duct 16 in conduit 18 to combustion section 20. Carbon values are completely consumed due to the addition of excess air, usually at least 1% to 25% and preferably 10 to 20% in excess of that required to convert the carbonaceous fuel to carbon dioxide and heat. The amount of excess air introduced depends on the nature of the carbonaceous fuel. As little as 1% excess air can be employed for gaseous to liquid fuels with at least 10% excess air being employed for normally solid fuels. 
     In addition to combustion zone 20, boiler 12 normally contains a radiant boiler section, a convection boiler section, and a high temperature economizer and may be followed by electrostatic precipitator 22 to remove fly ash. Other means to remove ash can also be employed. For instance, cyclone, bag filters and the like may also be employed. The air required for the combustion is blown into air preheater 24, and passes by duct 16 to the combustion zone, by conduit 18 normally at temperatures from 500° to 600° F. 
     A portion of the combustion products rather than utilized in transferring their heat by convection and radiation to boiler feed water are removed by line 26 from the high temperature section. The combustion gases will normally range from about 2000° to about 3800° F depending on the point of extraction. 
     The extracted gases which contain the carbon oxides as well as unconsumed oxygen pass to reactor 30 where there is introduced a hydrocarbon (H.C.) and a gaseous oxidant for the hydrocarbon to the extent the oxidant is not provided in the form of unconsumed oxygen in the extracted combustion gases. 
     The fuel employed may be carbon containing reactants capable of reaction in the gas phase at the temperatures provided without appreciable formation of soot. Exemplary of such fuels include hydrocarbons, methane, ethane, propane, the butanes, atomized or vaporized liquids and the like with natural gas preferred for reason of economy. Finely divided solid fuels such as coal and char may also be used. 
     The oxidant may be a source of oxygen, typically air or oxygen of higher purity than air and/or steam. 
     The extracted high temperature gas serves as a media to initiate and promote the thermal conversion of the hydrocarbons to hydrogen and/or its equivalent carbon monoxide in a stoichiometric deficiency of the oxidant. The principle reactions to occur are (1) to (4) above with reaction (1), for instance, being generalized, depending on the hydrocarbon to: 
     
         C.sub.n H.sub.m + (n/2 + m/4) O.sub.2 → n CO + m/2 H.sub.2 O (5) 
    
     in addition, carbon dioxide to the extent present may reduce to carbon monoxide increasing conversion efficiency based on the hydrocarbon fed to, under certain circumstances, over 100%. 
     The amount of carbon containing fuel fed will provide a total equivalent of from about 5 to about 100, preferably from about 15 to about 50 mols of carbon and H 2  as present in the feed per 100 mols of extracted gas. For example, a mole of metrane is equivalent to one mole of carbon and two moles of H 2 . The amount added is dependent on and proportional to temperature of the flue gas. Effective conversions of over 100% are realized for hydrocarbon feeds of 10 mols or more per 100 mols of flue gas. Reaction is allowed to be carried out adiabatically to a new but somewhat reduced temperature. High purity oxygen can be used to avoid contributing nitrogen to the product and may not become involved in CO 2  production. 
     The product reducing gas contains appreciable hydrogen and/or its equivalent carbon monoxide. The latter forms hydrogen on reaction with water via a water-gas shift reaction. 
     To the extent the products of the combustion are not extracted, they are used for power generation and exhausted to stack 32. 
     Some of the advantages of my process are that the heating fuel source is inexpensive coal or residual fuel oil used to fire the boiler. No heat transfer surfaces of expensive metals are required and no catalyst that may be susceptible to poisoning or subject to carbon deposition, are required, and accordingly the process is inherently cheaper, more flexible and more rugged. If, however, more rapid reaction rates, particularly at temperatures below 2000° F are desired, a catalyst may be employed but then, the usual precautions must be observed to guard against poisoning or masking the catalyst. 
     Another advantage of this invention is that heat from the combustion gases can be transferred most efficiently and economically to produce steam at the high temperature and the gases extracted after cooling, at the desired temperature for the efficient promotion of reactions (1) or (3). Reaction (4) serves only to increase the temperature of the reaction mix. 
     EXAMPLE 1 
     To an extracted flue gas mixture shown below there is added natural gas (shown as CH 4 ) as follows in Table I. 
     
                       Table I______________________________________        Flue Gas   CH.sub.4 Stream        Lb. mols/hr.                   Lb. mols/hr.______________________________________CH.sub.4       --           5.0CO.sub.2       14.45H.sub.2 O      8.58O.sub.2        2.70SO.sub.2       0.27N.sub.2        74.00          100.00Pressure PSIA  14.7         14.7Temperature ° F          2500         60______________________________________ 
    
     The adiabatic reaction temperature achieved is 2367° F and the equilibrium composition of the product gases is shown in Table II. 
     
                       Table II______________________________________             Lb. mols/hr.______________________________________  CO           9.42  COS          0.01  CO.sub.2     10.02  H.sub.2      4.57  H.sub.2 O    13.85  H.sub.2 S    0.16  N.sub.2      74.00  SO.sub.2     0.05  S.sub.2      0.02  S            0.01  Total        112.11______________________________________ 
    
     EXAMPLE 2 
     With the flue gas mixture as in Example 1, there is added 10 mols of CH 4 . The adiabatic reaction temperature reached is 1742° F and the product gas consisted of the following components shown in Table III. 
     
                       Table III______________________________________              Mols/hr.______________________________________  CO            16.77  COS           0.01  CO.sub.2      7.67  H.sub.2       17.02  H.sub.2 O     11.30  H.sub.2 S     0.26  N.sub.2       74.00  Total         127.03______________________________________ 
    
     While in Example 1, 9.42 mols of CO and 4.57 mols of H 2  were formed for a total of 13.99 mols or 93.3% conversion efficiency based on reaction (3) above, in this Example 43.79 mols of CO + H 2  were formed from 10 mols of CH 4  or 146% conversion efficiency based on reaction (3). This is due to the reduction of part of the CO 2  to CO. 
     EXAMPLE 3 
     The flue gas of Example 1 is extracted at 3500° F instead of 2500° F. There is added 15 mols/hr of CH 4  instead of 10 mols/hr. There is achieved a mix temperature above 2000° F. The mix is far removed from the conditions for carbon formation. Table IV shows the reactant, product gas composition and operating conditions. 
     
                       Table IV______________________________________       Reactants     Product Gas       Mols/hr.               Mols/hr.  Mols/hr.______________________________________CO                                25.26COS                               .01CO.sub.2      14.45               4.18H.sub.2                           28.53H.sub.2 O     8.58                9.79H.sub.2 S                         .26N.sub.2       74.0                74.00O.sub.2       2.7SO.sub.2      0.27CH.sub.4                15.0         100.0     15.0      142.03Pressure PSIA 14.7      14.7      14.7Temperature ° F         3500      60        2025______________________________________ 
    
     In this Example, the yield of H 2  + CO was 53.79 mols/hr. or 120% yield efficiency based on reaction (3) above. 
     EXAMPLE 4 
     In this Example, steam is used as the oxidant. The composition of the feed and product gases and net conditions are summarized in Table V. 
     
                       Table V______________________________________     Reactants            Hydrocarbons     Flue Gas            + Steam Mols/                         Product Gas     Mols/Hr.            Hr.          Mols/Hr.______________________________________CO                                21.43COS                               .01CO.sub.2    14.45                 8.01H.sub.2                           32.35H.sub.2 O   8.58     15.00        20.95H.sub.2 S                         .26N.sub.2     74.00                 74.00O.sub.2     2.70SO.sub.2    0.27CH.sub.4             15.00Total       100.00   30.00        157.1Temperature ° F       3500     212          1873Pressure PSIA       14.7     14.7         14.7______________________________________ 
    
     The conversion efficiency of CH 4  to CO + H 2  for Example 4 is the same as for Example 3, i.e. 120% based on Equation (3). 
     The foregoing invention is not limited to boiler flue gases but may be applied to any process where a gas is available at a high temperature such as smelters, roasters, lime kilns, cement kilns, blast furnaces and magenetohydrodynamic power generating channels and the like.