USRE15211E - Process fob the production of alcohol from gas containing ethylene - Google Patents

Description

C. A. BASURE. -PROCESS FOR THE PRODUCTION OF ALCOHOL FROM GAS CONTAINING ETHYLENE.

' APPLICATION FILED SEPT. 2, I921.

Reissued Oct. 25, 1921. 1 5,2 1 1.

i I 63 I 6 6)] I Z L U l I! 1a I6 I x INVENTOR debunk 19. Boa

ATTORNEY PATENT OFFICE.

OLEBU RNE A. BASOBE, OF AUBURN, ALABAMA.-

rnoc'nss'roa m raonccrron or ALCOHOL raou GAS couramme nrnrrm.

Specification of Reissued Letters Patent. Reissued Oct, 25, 1921,

Original No. 1,885,515, dated July 28 1921, Serial No. 452,285, filed March 14, 1981. Application for reissue filed September 2, 1921. Serial .No. 498,161.

To all whom it may concern:

Be it known that I, CLEBURNE A. BAsoRn,

a citizen of the United States of America, residin at Auburn, inthe county of Lee and State 0 Alabama, have invented certain new and useful Improvements in Processes for the Production of Alcohol from Gas Containin Ethylene, of which the following i a specification.

V This invention relates to a novel process for the production of alcohol from by-product coke oven gas or other gas containing ethylene, the tar, ammonia and light oil of which has primarily been removed during the lant process in which gas is made.

y invention contemplates the 'prelimi-- nary treatment of'the gas so as to remove therefrom the hydrogen sulfid, water and preferabl the carbon dioxid and it is then scrubbed y causing it to bubble through hot concentrated sulfuric acid to'produce ethyl hydrogen sulfate as a resultant compound in-the scrubbers while the gases pass off to the service mains for commercial use, practically unaffected by the removal therefrom of t e ethylene. The ethyl hydrogen sulfate is then admixed with a predetermined and definite quantity of water, which is restricted to the proportion necessary for the contemplated reactions and no more. The resultant mixture'isthen subjected to heat in a suit- I able closed apparatus which will maintain for a predetermined length of time the requisite temperature conditions for the uniting of" the ox en and hydrogen in the water with the (Ki-I, of the ethyl hydrogen sulfate to form alcohol and when this reaction is substantially complete, which requires aproximately one hour, the resultant product 1s distilled and condensed in any well known mannerand the alcohol recovered, the extent to which it .is diluted being controlled and limited by the control of the volume of water added to the ethyl hydrogen sulfate.

One distinctive feature of my invention relates to the length of time provided for the reaction in which the alcohol is formed, which length of time is preferably obtained under roper conditions by heating the mixture 0 water and ethyl hydrogen sulfate in a closed vessel under a temperature preferably ranging between 100 and 120 C. In

my experiments I have found that the reaction in which the OH from the'water. unites a with 0 H, in the ethyl hydrogen sulfate to produce C H OH (alcohol) is one that develops rather slowly and to obtain the maximum production of alcohol it is essential that this reaction shall have am le time to proceed to a finish. Bearing in mind thatit must be conducted in the presence of heat I have concluded that the most practical way to complete the reaction is in a vessel where the desired tem rature conditions can be maintained indefinitely, should it be necessary; I have determined by experiment that the reaction under a temperature of approximately 110 C. is ordinaril 'completed in from to minutes. W en the reaction has been thus completed the final step of distillation'and condensation for the recovery of the. alcohol and. for the recovery of the sulfuric acid for reuse in thescrubhere, can proceed in any well known manner. As a result of the control of the reaction in question, I am enabled to obtain the maximum alcohol output from the original constituents.

Another distinctive feature of my invention is based upon the control and definite limitation of the volume of water added to the ethyl hydrogen sulfate. Heretofore it.

ha been attempted to treat ethyl hydrogen sulfate with steam, and alcohol to a limlted extent has been obtained in this manner, but

the process has never gone into general use because the requisite time for the completion of the reaction was not rovided for and there was nocontrol or imitation of the. volume of. water added in the form of steam and as a result of the latterfact the relacent. in volume of water to the other ele-.

ments, will produce the most satisfactory operating results.

I have also discovered that when the degree of concentration of the ethyl hydrogen sulfate in the crubbers is permitted to exceed 30 per cent. by weight of the sulfuric acid in the scrubbers, then the subsequent dilution and treatment of such concentrated produce ether in substantial quantity which will increase as the concentration of the ethyl hydrogen sulfate increases. I prefer to draw off the acid andethyl hydrogen sulfate for my proposed treatment when the "glass or inert particles ,12 therein. These ethyl hydrogen sulfate reaches a concentra tion of between 10 per cent. and 20 per cent. by weight of thesulfuric acid.

In describing my process from the initial stage, utilizing by-product coke oven gas free from tar, ammonia anddight oil, as a source of ethylene, referenceis made to the drawings which illustrate a typical apparatus to which this gas, in accordance with well known practice, after being freed of its hydrogen sulfid, water and preferably its carbon dioxid, is presented in heated condition to centigrade) through a pipe or conduit 1 and enters either end scrubber of a series of scrubbers 2 which are charged with concentrated sulfuric acid and filled with broken particles 3 of inert matter such as coke, rock, etc. The gas which is under pressure is caused to bubble up through the tanks passing therethrough in series and the tanks are heated by any suitable burner equipment 4 or by superheated steam in chamber 5. The principal of counter-currents is used in the scrubbing. From the final scrubber the coke oven gas, freed of its ethylene, passes through the conduit 6 from the end scrubber of the series under control of its respective valve 6 to the Service main, while the ethyl hydrogen sulfate formed by absorption of ethylene in concentrated hot sulfuric acid (66 B. preferably heated to 70 to 80 C.) is drawn off from the first scrubber, or any combination as first and second, through oneof the pipes 8 and conducted past a valve 9 in each pipe 8 into a heating vessel 10 which is typically illustrated and may be' of any suitable type. After drawing the ethyl hydrogen sulfate and sulfuric acid from a scrubber. the latter is then refilled with acid and made the last of. the series. This heating vessel is preferably heated by side burners 11 ourrounding the same opposite the liquid level therein and has a small amount of broken particles and the side burners are especially employed forpreyenting the foaming of the reacting liquids 1n the apparatus. densing coil 13 is connected by a pipe 14 to the top of the vessel 10 and is controlled by -a valve 15. This condenser coil discharges into a collecting funnel 16which is adapted to collect the recovered alcohol. 'A

pipe 17 is used toconductthe sulfuric acid from the vessel 10'under control of valve 18 into filter 19, whence the liquid'passes by a Superheated steam for .the purpose of steaming residual sulfuric acid is supplied to the'ves- A conthe ethylene in the scrubbers.

s; 10 by means of a pipe 22under control of valve 23, and water is supplied to said vessel through pipe 24 under control of valve 25.

-When the ethyl hydrogen sulfate has reached the desired degree of concentration in the sulfuric acid (10% to 20% weight thereof) it is readyfor treatmentin the heating vessel 10 and it is delivered.

thereto'through one or more pipes 8 by opening their respective valves "9, the valves 15., 18 23 and 25 being previously closed and the valves 9 being closed after the admission of the. ethyl hydrogen sulfate and sulfuric acid. The water in volume approximately- 60 per cent. of the volume of ethyl hydrogen sulfate and sulfuric acid is then supplied:

The uniting of OH with 0 H, to form alcohol takes placeslowly and hence is best accomplished in a closed heating apparatus for the requisite time before commencing the distilling and condensing operations. At

the completion of the reaction, valve 15 to the coil is opened and the vapors, consisting of alcohol, water and some sulfur dioxid, pass through the coil and the alcohol and Water are condensed until all of the available alcohol is recovered. The sulfurdioxid gas, largely uncondensed, may be used for removal of the hydrogen sulfid from the raw 2H S+SO,=2H O+3S,

water tank 30 or by liquefaction. After this live steam can be admitted through pipe 22 in sufiicient volume to conagulate the colloids in the remaining sulfuric acid and the [latter canthen be drained off through the filter and thereby relieved of its foreign matter except the water which is removed in the The resultant 7 product is substantially pure acid. The alcohol with its surplus water content and sulfur dioxid is then treated in any well known manner for the elimination .of the water and'sulfurzdioxid and the resultant evaporating mechanism 21.

product is pure commercial alcohol.

V. I have also foundfthat the. successful:

operation of thefprocess is dependent upon the slow and uniform feed of .the'gases to" I the scrubbers, any suitable regulating means,

as valve 26, being provided to feed it slowly v enough to' efiectthe substantial removal of Care should volume of water added and for. the time of the reaction in the heating apparatus 10 are those which my experiments have found to be most satisfactory, it is, nevertheless, to be understood that these may be varied within the scope of my invention and with approximate results roportionate tothe departure from those gures and proportions which I have found most suitable.

This application is a continuation in art of my application Serial No. 417 ,224, led October 15th, 1920.

Having thus described my invention, what I claim as new and desire to ters Patent, is

1. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding to sa1d mixture water in excess of 50 per cent. of the volume of'said mixture, subjecting theresultant reacting constituents to heat in a closed vessel, then distilling off the alcohol and water, and

condensin the alcohol.

he herein escribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding to said mixture water in amount equal to from 50 per cent. to per cent. of the volume of the said mixture, subjecting the resultant reacting constituents to heat in a closed vessel, then distilling oil the? alcohol and water, and finally condensin the alcohol.

3. he herein escribed process for the ,production of ethyl alcohol from a mixture ,of sulfuric acid and ethyl hydrogen sulfate,

which 1 consists in adding to said mixture water in amount equal to approximately 60 per cent. of the volume of the said mixture, subjecting the resultant reacting constituents to heat in a closed vessel, then distilling off the alcohol and water, and finally condensing the alcohol.

4. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding to said mixture water in excess of 50 per cent. of the volume of said mixture, subjecting the resultant reacting constituents to heat in a vessel to continuously volatilizh and recondense them therein until the combination of CJIJISO, with HOH is substantiallycomplete, then distilling off the alcohol and water, and finally condensing the alcohol.

he hereindescribed. process for the secure by Let which consists in adding to said mixture water in excess o'f'50 per cent. of the volume of said mixture, subjecting the resultant reacting constituents to .heat in a vessel to continuously volatilize and recondcnse them 'therein for approximatel 60 minutes, then distilling off the alcoho and water, and finally condensing the alcohol.

6. he hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding to said mixture water in amount approximately equal to 60 per cent. of the volume of the said mixllure, subjecting the resultant reacting constituents to heat in a vessel to continuously volatilize and recondense them therein for approximately 60 minutes, then distilling offthe alcohol and water, and finally condensing the alcohol.

7. The hereindescribed process for the production of alcohol from gas containing ethylene, which 'consists in treating the as with hot concentrated sulfuric acid 66 7 0 to 80 C. to form ethyl hydrogen sulfate not in excess of 30 per cent. in weight of the acid in the mixture, adding to the ethyl hydrogen sulfate and sulfuric acid a volume of water approximately 60 per cent. of their combined volume, treating the resultant compound in a closed heating apparatus until the reaction. involving the uniting of the hydroxyl radical with the 0 H in the ethyl hydrogen sulfate to form alcohol is practically completed, then distilling oil and condensing thealcohol.

8. The hereindescribed process for the production of alcohol ethylene bearing gas free of tar, ammonia and light oil, hydrogen sulfid, Water, and preferably carbon dioxid, which consists in treating the gas with hot concentrated sulfuric acid 66B. 70 to 80 C. until the concentration of ethyl hydrogen sulfate in the sulfuric acid has reached a degree of from 10 per cent. to 20 per cent. by Weight of theacid in said mixture, drawing off the ethyl hydrogen sulfate and sulfuric acid from the scrubbers, admixing with) the latter an amount 'of Walter. approximately 60 per cent. of the volume of -the ethyl hydrogen sulfate and sulfuric then distilling off and condensing the alcof hol, substantially as described.

9. The hereimlescribed process for the producticuof ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding water to said mixture in volume not less than 50 er cent. of the volume of the mixture, hol ing the resultant mixture under heat in a vessel until the combination of 0,H,Hs0, with HOH is v oil and condens' of the volume of the mixture, holdin '11. The hereindescribed' proc ss f the substantially complete; and. then distilling dilute alcohol.

10. The herein escribed prom for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen Sulfate,

which consists in adding water to said mixture in volume between 50 and 70 per cent; the resultant v mixture under heat unti the lydroxylradical has combined with the ,H gradical, and then distilling all and condensing dilute alcohol.

production of ethyl alcohol from a mirture man of Sulfuric acid and ethyl hydrogen we. in which the latter is less than 30' per cent.

by weight of the former, which consist; in adding water to said mixture in volume not less than 50 er cent. of the volume of the mixture, hol 1n the resultant mixture under heat in a vesse until the combination of C,-H,HSO with HOH is substantiall complate, and then distilling of and con ensing dilute alcohol.

In testimon whereof I afiix ,witnex Noum Wmn.

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