USRE18382E - William w - Google Patents

Description

W. W. ODELL PROCESS FOR MAKING COMBUSTIBLE GAS March 8, 1932. Re. 7 18,382

Original Filed March 4. 1927 IIIIHH IIIIIIH Reis sued Man 8; 1932 UNITED S ATES PATENT: OFFZICE' WILLIAM woman, or NEW YORK, N. Y., ASSIGNOR 'ro COLUMBIA ENGINEERING Am: MANAGEMENT oonronnrron', or cmcm m'rr, 01110, A oonrom'rron 017.0310

' v '5 rnocnss r03. MAKINGCEMBUST'IBLE GAS Original No. 1,762,106, dated June}, 1930, Serial No. 172,736, filed March 4, 1921. Application I is sue filed November 25, 1931. Serial. No. 577,370, 1

In essence, the process consists in generating combustible gas containing hydrogen and carbon monoxide, using one or more hy 'drocarbons of the paraflin series as a fuel for the generation ofat least a part of it; natural gas beingv a ready and low priced source of part of the process is based upon the chemical reactions occurring when the parafiin hydrocarbons are .subjected E0 the action of heat,-i. e., when they are caused to contact 7 heated surfaces, particularly in'the presence of steam; the contacting surface may be carbonaceous or other substance.

The objects of my invention are:

1. To utilize economically the paraffin hydrocarbons which in the natural-gas fields are so frequently wasted.

2. To produce a gas, using said hydrocarbons, which'will have the right proportional amounts of carbon monoxide (CO) and hy-' drogen- (H for the synthetic production of methanol, i. a, about 2 parts of H to one part of CO, since the methanol reaction is represented by the equation 1 oo+en =onaon 3. To provide a flexible means of produc 'ing gas of standard quality using p-araffin hydrocarbons, in chemicalreactions, in the generation of a part thereof.

' 4. To produce water gas with higher efliciency and at a lower cost than when using solid fuel aloneibythe use of said hydrocarbons in chemical reactions. I

5. Toutilize and recover in the'combustible as made a large portion of the volatile comustible matter of a bitumiiniferous or other water-gas the new and improved oil-cracking processes so much of the'low-density hydrocarbons are formed that a limitjhas been put upon the amount ofthe latter whichean be present in natural-gas gasoline used in blending; and

-for rethis has resulted. in very recent months, in

the availability of large quantities of C H- C H (LH which can be obtained either in a high degree of purity or mixed with each other or with methane. The propane (C ll and butane (C H are now wasted to a large I extent by being burned in pilots in some of the natural gas fields even in those' fields where the methane and ethane are piped to centres of consumption.

I find it possible to produce'hydrogen and carbon monoxide, using the paraflin hydrocarbons, at a lower cost than when using solid fuel oilly at nominal prices, and without the formation of free carbon.

The chemical equations of interest and {vhich are alluded to hereinafter are as folows:

effect of completely cracking the paraflins by the application of heat; Equations 6 9 1nclusive show the effect of heating them in the presence of sufficient steam to combine wlth the carbon by the water-gas reaction as shown in Equation 10. Equations 11 to 14 inclusive are respectively combinations of 6, 7, 8 and 9 with Equation 10. It will be observed that in.each of these combination equations the volume ratio of H to CO in the products of reaction is 2 to 1, which is a desirable proportion for the production of synthetic methanol by Equation 1. It is obvious then that in the generation of the idealwater-gas (CO-i-H mixture); using para'ifin "hydrocarbons there is a preferred proportion of.

I In the above there are three classes of reactions; Equations 2 to 5 inclusive show the tion-equations 11 to 14. In common practice in generating water-gas amuch larger amount of steam is necessarily used than enters into thechemical reaction and this will hold true in this instance. Therefore in controlling the reactions 11 to 14 it is necessary to use substantially that quantity of the hydrocarbons which will increase the volume ratio H to CO above that of Equation 10, in which the ratio is 1 to 1, and preferably a suflicient amount to make the ratio 2 to 1, when making a gas for use in synthesizing methanol. This ratio can be varied at will within certain limits; Equation 6 shows the conditions for a ratio of 3 to 1 and the other equations show smaller ratios; that in' Equation in'which no hydrocarbons enter the reaction, being to 1. The low limit is about 1 to 1, but there is giractically no upper-limit ratio short of in nity when reactions 2 to 5 are considered. The latter reactions do not re resent efiicient gasification and are not of t emselves new.

1 5 The process of making .water gas(CO and H mixtures having a hydrogen-carbon monoxide ratio of substantially 2 to 1 by the high temperature reactions represented by Equations 11, 12, 13 and 14 or combinations of them, using1 a. substantially definite proportion of hy rocarbons, steam and carbon in the reactions as shown, is believed to be a new combination in the' art. It will be noted that ropane (C H and butane 86 (C4H 5) yiehfa gas, by reactions represented in Equations 8 and 9, which is quite satisfactory for the production of methanol (CH,OH)'. Thus it is apparent that the reaction shown in Equation 10, commonly known as the water-gas reaction, need not enter into or become a part of the reaction producing a mixture of H and (JO-other than in the conversion of the carbon of hydro- I carbons to (JO. In other words, additional carbon is not necessary. Also it is to be noted that the gas generated is substantially free fromsus'pended carbon thereby making it unnecessary to treat the gas for the remova of carbon.

The apparatus in which-I am able to make gas by my process is shown in Figure 1. Figure 1 is a front elevation of a suitable gas generator set, with ortions of the shells cut away to show the interior in section for clear- 55 ness. The enerator is shown connected with double 0 ecker chambers such as the carburetor and superheater of a carburetted water-gas set, but obviously it can function without the latter.-

In Figure 1, 1 is the generator shell having charging door 2 for charging solid fuel or other contact material shown at 4 and supported by grate bars 3. The steam supply .line is shown at 5, having inlet control valvesfor up and down-run steam respectively at :6 and 7. Hydrocarbon gas is supplied to the 2 generator through supply-line 8, having inlet control valves 9 and 10. V The ofitakes for finished gas areshown at 11, 12 and 12,, and the respective control valves are shown at 13, 14 and 14 Air is sup lied through inlet 15 and control valve 16. he -checker chambers 17 and Bare so connected that gas from 13 ,and 14 can be passed through them and out through ofi'takes 21 and 22 by controlling valves 23 and 24. A connection for hydrocarbon gas is shown at'19 with control valve 20. Checkerbrick or contact material is shown at 25 and 26 and a steam. control valve at 27 for introducin steam into chamber 18.

Secondary air is a mitted through 28 and 29, and enriching oil" or other carburetting material, is introduced through 30 and 31.

A steam inlet for cooling back-flow gas and valves is shown at 35.

Before describin the operation 15 my process I call attention to the fact that in the manufacture of water gas or carburetted wator is much lower using bituminous coal ter-gas the gas making capacity of the gener-' than with coke, and this difl'erence isdue to gas, in cycles as follows: Referring to Figure 1, the ignited fuel 4 is air-blasted to 'incandescence by opening valve 16 and admitting air through 15, the blast gases being burned in chambers 17 and 18 by the air introduced through 28 and 29 and then discharged through 11, 13, 17, 18, 21 and 23. The air blasting is discontinued, valve 16 is closed,

cap 23 is closed and valves 6 and 24 are opened, valve 13 remaining open, and a reg ular steam run ismade. Either alternate up and down steam-runs aremade or splitruns are made during the steaming periods;

one air-blasting and one steaming period making a complete cycle. The cycles are repeated. When down steam runs are made, valves 6,

13, and 13 are closed and valves 7 and 14 are opened. During the admission of steam during the up-runs, hydrocarbon gas is also admitted to the fuel bed by 0 ening valve 10. In this manner less solid fuel is consumed in the generator during the steam-run periods,

less 15 used per thousand cubic feet of gas -made, and therefore the rate of travel of i the generator fuel downwards by reason of its consumption is decreased. Accordingly the,

fuel in the upper zone becomes hotter than i it would without the addition of the hydrocarbon gas. This eflect becomes more evident upon comparing Equations 6 and 10.

-. Equation 10, and more heat is carried from the hot zone to the upper cooler zone of the generator by this increased volume of gas.

The hydrocarbon gas may be introduced durin each up-run,durin a portion of each run, uring both up and own runs, or during a certain, predetermined percentage of the total number of runs. excess of hydrocarbon gas may be used, that is, beyond the normal end of the steam run period. In the'latterperiod the gas is not appreciably cracked and functions chiefly as a heat-carrying agent, helping to equalize the temperature in the generator fuel-bed, and simultaneously carburetting the fmake gas. When a mixture of parafiin hydrocarbons are introduced into the generator.

fuel bed, as through 10 during a prolonged part of an up-run, the higher members' only of the series are appreciably cracked. In this manner the amount of cracking and the na- 25 ture of the finished gas can be predetermined.

Attention is called to the fact that the heat absorbed in the generator according to Equation. 6 is much less than is absorbed by Equation 10, hence for a definite temperature condition in the generator fuel-bed the quantity of gas which can be made according to the former is more than double that which can be made accordin to Equation 10. Similar comparisons can e made between Equation L .only is the capacity of the generator in creased when using coal as fuel and the gasification efficiency raised above that'of-normal practice, but the overall efliciency in maklng carburetted water gas and employing hydrocarbon gas as described is higher than other processes using hydrocarbons, such as the combined oil-gas, reformed gas process and the like, so far as I am aware.

So far, the use of hydrocarbon gas on the up-runs only, has been discussed. It can be used when desired'on the-down-.runs as well, but when usin coal as 'genera'torfuel it should not be admitted cold=to the to generator fuel, although with coke 1161 this can be satisfactorily done. Means are providedfor introducing the hydrocarbon gas through valve 20 and inlet 19, and steam through 27,when using'coal in the generator. In this manner the gas, andpreferably, the steam also are preheated before reaching the fuel bed. In fact a considerable amount of reactions 6, 7 8 and 9-takes' place in the checker chambers 17 and 18 before reaching the gen- 'erator fulsbed'. To a large extent the amount of carbon (generator fuel) consumed during therun when operating inthe manner described above is controlled by varying,

gas use a large vproportion of hydrocarbon gas there Furthermore, an

of the of the the pro ortions of steam and hydrocarbon When using coke fuel and using is a tendency for the fuel in the upper part of the fuel bed to become too. hot. Under these conditions thehydrocarbon gas is ad- *mitted to the generator from above the fuel bed, i. e., through valve 9, the steam being admitted through valve 7 and the make gas being removed through14'0r 14 as desired.

In the generation of gas for use in manu facturing synthetic methanol, when the proportion of CO and H must be held ithin fixed limits and when the latter gases ar preferred to the exclusion of other gases it is necessary to operate with fuel-bed temperatures well above the dissociation or reaction temperatures; this is provided for by adjusting the amount of air used with respect to the steam and hydrocarbon gas. used; short 35 cycles are used under these conditions. After the generator is in operation it is only neeessary to analyze the generated gas to determine whether or not the cycle should be yond that shownin Equations 6 to '14 it is 10!? only necessary tomaterially reduce the amount of steam used and allow reactions 2 to 5 to take place accbrding to the .hydrocarbonused. I

The parafiins are not theonlyhydrocarbon gases which can be used inthe production of v mixed CO and H by'chemical reaction with steam; they are mentioned in particular because they are commercially. available in large quantities. Ethylene (C' H a by product in the cracking of petroleum in the manufacture of gasoline is also a suitable hydrocarbon for the purpose as shown by the following equations:

The higher olefin gases react in a similar of CO and H for Equation '1, hence for the latter purpose, when using H, in the generator it is desirable to consume as little generator fuel during the steam run as possible and .to adjust the steam and 0 H, propor- 5 tions so that the make gas is substantially as shown in Equation 16. One of the 'funda-- mentals of my process, then, consists in: causing steam and hydrocarbon gas to be introduced simultaneously into an incandescent mass of solids, which mass may or may not comprise coal, coke or the like and causing said steam and gas to react chemically indefinite proportions which are substantlally and at least one molecule of H 0 for every carbon atom resent in the reacting hydrocarbon'gas. he complete cycle of operation, using a multiple-shell set, as shown in Figure 1, and using hydrocarbon gas on both the up and down runs is substantiallyas follows: Up blast the ignited fuelin the generator w th air until it is incandescent, meanwhile conducting the blast gas into the attached checker chambers, burning it therein by the addition of secondary air admitted through i u 29 and causing the burned gas to pass out of said chambers through 23; discontinuing the air-blasting and introducing both steam and hydrocarbon gas from beneath the fuel bed, removing the reaction products from above the fuel bed and causing them to pass through the checker chambers; discontinuing this steam run and repeating the cycle, except that, the subsequent steam run is made as follows:

Steam and hydrocarbon gas are introduced into the top of the superheater in molecular proportions, caused to react at least in part m the checkerchambers and conducted into the generator fuelsbed from above it, the finished" gas being removed from beneath the fuel bed through 12 and 14 Obviously, instead of making alternate up and down runs, split runs can be made or a combination of split runs and up and down runs; this is a common practice in water-gas generation. Like-- wise, steam alone may be used during some of the runs, omitting'the hydrocarbon twin order to correct any deviation from t e selected or desired percentages of carbon monoxide and hydrogenin the finished gas.

When it is-intended to usethe-gas made as .city gas, enricher may be to the makegas flowing through thechecker chambers or elsewhere. If oil is used as enricher it phere of CO-l-H; than in the oil-gas process;

the efficiency of gasification in the latter pro-' eess being less than per cent, whereas with the same gas oil the gasification efiiciency in the crackin of said oil in an atmosphere of CO-t-Hg is 0 r cent or more. When 'suflicient hydrocar n gas is available, I refer to enrich the CO+H mixture by int ucing the former into the latter in the checker chambers. 'A special inlet for it is not shown for simplicity, since about the same result 13 gas can be made in the generator essentially 'of 1750 to1'900 degrees Fahrenheit are satis .filler for the generator, and is a splendid concanbe cracked more efliciently in the atmosobtained by openin valve 9 on the up runs and valve 10 on the own runs. This method of introducing the enricher tends to keep valves 13 and 14 cool.

There are conditions and localities in this country where it is necessary to alter the gas making process used in-generatingcity gas because of a variation in the supply ofnatural gas and *varation in demand for gas. Ibclieve I have a flexible unit which may be subjected to considerable variation in o eration without materially altering the qua ity of the finished gas. For example, in the apparatus shown in Figure 1,' water-'gas can be madein the generator almost entirely from so hydrocarbon gas, such as natural gas, and enriched with natural gas when the supply of the latter is suflicient to. meet the demand. On

the other hand, when this supply is low, water from solid fuel, using'the natural gas for enriching only; in extreme cases the enrichin can in part be done by introducing gas 01 into the checker chambers, as in the standard carburctted water-gas process. It may be done by introducing hydrocarbon gas through 10, or 9 on up and down runs respectively during the latter part of the steam runs.

In making straight CO +H mixtures, con- .95 taining only small percentagcs of other gases, from hydrocarbon gas as a base raw material, or from both hydrocarbon. gas and solid generator fuel, the temperature of the checker bricks in'chambe'rs 17 and 18 should be appreciably higher than is common practice in making carburetted'wateras. The temperature should be preferably, a ove 1700 degrees Fahrenheit; average temperatures 103 factory. When gas oil is used and a carburetted gas, such as city gas, is made, lower temperatures are more satisfactory, namely, 1400 to 1550 degrees Fahrenheit. The latter is also true when carburetting by introducing hydrocarbon gas into the gas entering checker chambers 17 and 18 from the generator.

Coal, coke, or the like, is a satisfactory tact medium or carrymg on reactions as rep- 115 resented by Equations 2 to 17 inclusive.

- -When it is desirable not to completely crack all of the hydrocarbon gas used inthe process, and yet to maintain hi h temperatures in the chambers 17 and 18, t e operation is so conducted that the gas produced in the generator does not pass throu h chambers 17 and 18-.. In this manner the c ecker bricks in the latterchambers can be used to full advantage for producing" carbon monoxide and hydrogen from steam and hydrocarbon gas by admittingthe latter materials respectively through 27 and 20. .Th complete operation" is as follows: first, air-blast fuel 4 with air through 15, conducting blast gas in- Q and any'excess of either gas or steam or both to checker chambers 17 and 18, throilgh 13, simultaneously admitting secondary air to 17 through 28' for combustion of the blast gas, discharging the roducts of combustion through 21 and 23. ow discontinue the air blasting, close stack 23 and introduce steam through 6 and hydrocarbon gas throu h 10, taking'the'resultmg roduct 01f throug 13 admitting hydrocar on as to generator through 9 also when enriched ing as just described and then, when the generator fuel 4 and the checkerbricks 25 and 26 are sufiiciently hot, discontinuing the airblasting, closing stack 23", introducinsteam and hydrocarbon gas simultaneously t rough 27 and 20 respectively, causing them to react chemically during their passage through 18 and 17, conductln'g the reaction products out of 17 through the generator fuel-bed 4 and out of generator; the latter step may consist in passing the gaseous products from 17 through 13 and 11,,down through fuel bed 4 and out through 12 and 14 or, when 13 is closed, through 14, up through fuel bed 4 and out through 13 When said gaseous roducts from 17 are passing through soli fuel bed, either upwardly or downwardly, additional steam is introduced into fuel bed 4 simultaneously with them by opening respec tively-valves 6 and 7. When sufiic ent hydrocarbon gas is available it-is also introduced into the fuel bed 4 alon with the .steam and the gaseous products IOID. 17 by opening valve 10 before. up runs and valve 9 before down runs. Furthermore, when "the enriching is done withhydrocarbon gas,

both valves 9 and 10 are open during up and down runs, the extent of enriching in this instance depending upon therelative amounts of-hydrocarbon gas used in the reactions and introduced after the products have emerged ,from the fuel bed. I

My gas generating apparatus is so designed that a substantially constant quality of gas can be made therem, using varying relative amounts of steam and hydrocarbon gas in the process. The temperatures in the checker chambers '17 and 18 are maintained by the combustion of, blast gas therein,, but when,

necessary or desired additional gas is supplied thereto by-opening valve 9 during the ofthe' generator fuel 4.- e taken from generator upward air blastin Finished gas can through ofitakes and valves at top and bottom (above and below the fuel bed) as shown at 13 and 14 besides the nflitakes leading through the checker'chambers. It is common knowledge that both, hydro- -1gen and carbon monoxide when separately mixed with air are inflammable overa wide range of mixtures and that the maxim 5 rate of flame propagation through the hydro gen-air mixture 1s much greater than that as is desired.- A subsequent cycle is made byrst air-blast 2 tion thereto of mixed air and carbon monoxide. For this reason and beca'use of the'wide difl'erence in density between hydrogen and carbon monoxide, it is preferable that the gas made for use alone or enriched as city gas have a specific gravity within definite limits and burning properties that are not appreciably different from those of other ases for which it may be interchangeably su stituted. Accordingly;-the gasmade by reaction of the hydrocarbon gases with steam should not only be free from suspended carbon but .the hydrogen to carbon monoxide ratio should be confined within certain limits as shown,*

namely, from three to one, respectively, to two, to one respectively. This I accomplish,

in my processby controlling the amount of steam and hydrocarbon gas used, thedur'ation of the cycle whichis shown to be short,

and the temperature of the contact surface for reaction. The equations show substantially the results'I obtain.

1 prefer not to limit myselfto the use of particular hydrocarbons, since practically all hydrocarbons react similarly in an incandescent fuel bed' in the presence of, steam. An

atomized liquid hydrocarbon is considered to be a gaseoushydrocarbon.

Attention is called to the fact that it is not possible to air-blast a fuel bed to a uniform temperature throughout and that in m process a step toward this goal is made; t e-tem-' perature gradient throu hout the fuel bed,

operatin with the intr uction of'hydrocar- V bons wit the steam, is smaller than in norenerations', Because of the latter I am ena led to quite completely de vj compose unsaturated hydrocarbons and to mal water-gas generate from steam and hydrocarbons,

high degree of purity.

I do not claim as my own the ing the carburetion of water'- as by'th'e-addr cracking.

I claim: 1.] A process of generating gaswhich gas is of cold hydrocar on gas without step comprissubstantially free from suspended carbon resulting from hydrocarbon decomposition which consists in, introducing hydrocarbongas into amass of solid fuel heated to adegree sufficient to decompose the, hydrocarbon gas, simultaneously introducing steam there with in amount suflicient to effect substantial- 1y complete reaction with the hydrocarbon gas, thereby producin a gas comprising, es-

sentially hydrogen an carbon monoxide and in which the ratio of hydrogen to carbon monoxide is substantially from two to one to three to one.

2. A process of generating gas which is substantially freefrom suspended. carbon resulting from hydrocarbon decomposltion which consists in, introducing hydrocarbon gas into amass of solid fuel heatedto a demixed hydrogen and carbon monoxide of a gree suificient to decompose the hydrocarbon gas, simultaneously introducing steam therewith in amount suilicient to efi'ect substantially complete reaction with the hydrocarbon gas, thereby producing a gas comprising essentially hydrogen and carbon monoxide and in which the ratioof hydrogen to carbon monoxide is substantially two to one. v

3. A process ofgeneratin'g gas which gas is substantially free from suspended carbon resulting from hydrocarbon decomposition- -which consists in, introducing hydrocarbon gas of the paraflin series into a mass of solid uel heated to a degree suflicient to decompose the hydrocarbon gas, simultaneously introducing steam'thefewith in amount sufficient to efl'ect substantially complete reaction with the hydrocarbon gas, thereby producing a gas com-prising essentially hy- Y rogen and carbon monoxide and .in which the ratio of hydrogen to carbon monoxide is substantially from two to one to three to One. v

4; A process of generating gas which gas is substantially free from suspended carbon resulting from hydrocarbon decomposition which consists in, introducing hydrocarbon Lgasof the paraflin series into a mass. of solid i to one.

fuel heatedto a degree suflicient to decompose the hydrocarbon gas, simultaneously -intro- 'ducing steam therewith in amount suflic'ient to. effect substantially complete reaction with the hydrocarbon gas, thereby producing gas comprising essentially hydrogen and carbon monoxide and in which the-ratio of hydro: gen to carbon monoxide is substantially two V is substantially free from suspended carbon resulting from hydrocarbon decomposition.

. which consists in, introducing, hydrocarbon gas into a mass"of solidfuel heated to a degree sufiiclent to decoinposethe hydrocarbon gas and to a'temperature' sufiicient for a water gas reaction to occur, simultaneousl introducing steam therewith-in amount su 'ficient to eifect substantially complete reaction'with said hydrocarbon gas and simultaneous reaction with carbon in the said mass of fuel to theextentthat'the resulting gas' comprises hydrogen and carbon monoxide 1n the ratio ofsubstantiallytwo to one.

6. A process of generating gas which gas is substantially free from suspended carbon resulting from hydrocarbon decomposition which consists, in, introducing hydrocarbon 1 heat to a degree suflicient to decompose the hydrocarbon gas and to a temperature suflicient for a water gas reaction to w cur, simultaneously introducing steam therewith in aniount suflicient to efiectsubstan- -t1ally complete reaction with said hydrocar-v bon gas and simultaneous' reaction withcan hen the mass of fuel to the extent that v 1y two to one.

of generating gas which gas the resulting carbon monoxi e in the ratio 0 substantial- 7. A process of generating gas which gas is substantially free from suspended carbon resulting from hydrocarbon decomposition which consists in, introducing hydrocarbon gas into a mass of solid fuel heated to a degree sufiicient to decompose the hydrocarbon gas, simultaneously introducing steam there-' with in amount suificient to efiect substantially complete reaction with the hydrocarbon s comprises h drogen and gas, thereby producing a gas comprising essentially hydrogen and carbon monoxide and in which the ratio of hydrogen to carbon monoxide is substantially from two to one toithree to one, introducing into a stream of the hot gas tliusgenerated gaseous hydrocarbons in amount sufficient to produce an enriched gas being substantially city gas.

8. A rocess of generating gas which is substantially free from suspended carbon re-' 5 sulting from hydrocarbon decomposition which consists in, introducing'hydrocarbon gas into a mass of solid fuel heated to a deree suificient to decompose the'hydrocaron gas, simultaneously introducin therewithin amount siifiicient (to e ect substantially complete'reaction with the hydrocarbon gas, thereby producing a as comprising essentially hydrogen an carbon steam 1 monoxlde and in which the ratio of hydrogen to carbon monoxide is substantially two to one, introducing into a stream of the hot gas thus eneratedgaseous-hydrocarbons in being substantially city gas.

9. A process of generating gas which gas is substantially freefrom suspended carbon resulting from hydrocarbon decomposition, which comprises introducing a gaseous hydrocarbon into a mass of solid fuel heated to a degree sufiicientto decompose substantial amounts of said hydrocarbon, simultaneous- 1y introducing steam therewith in an amount 'sufiicient to react with a substantial amount of said hydrocarbon, thereby producing a gas the major portion of which is hydrogen and carbon monoxide and in which the ratio of the hydrogen to carbon monoxide is substantially from two to one to three to one.-

In testimony whereof. I aflix my signature.

W. 'ODELL.

amount su cient to produce an enriched gas fie of the araflin series into a mass of solid flac 1

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