This patent from 1933 describes a process for producing acetic acid from ethyl alcohol using a copper oxide catalyst. Key points:
- Ethyl alcohol vapor is passed over a heated, specially prepared non-luminous copper oxide catalyst in the presence of oxygen to produce acetic acid.
- The catalyst is activated prior to use by treating it with alcohol vapor at high temperatures. During the process, the oxygen keeps the catalyst in an active condition so it can be used continuously without removal for reactivation.
- In a demonstration, 262 grams of 95% alcohol were passed through a copper oxide column at 300-340°C before the production of acetic acid peaked. The process yields high amounts of acetic
This patent from 1933 describes a process for producing acetic acid from ethyl alcohol using a copper oxide catalyst. Key points:
- Ethyl alcohol vapor is passed over a heated, specially prepared non-luminous copper oxide catalyst in the presence of oxygen to produce acetic acid.
- The catalyst is activated prior to use by treating it with alcohol vapor at high temperatures. During the process, the oxygen keeps the catalyst in an active condition so it can be used continuously without removal for reactivation.
- In a demonstration, 262 grams of 95% alcohol were passed through a copper oxide column at 300-340°C before the production of acetic acid peaked. The process yields high amounts of acetic
This patent from 1933 describes a process for producing acetic acid from ethyl alcohol using a copper oxide catalyst. Key points:
- Ethyl alcohol vapor is passed over a heated, specially prepared non-luminous copper oxide catalyst in the presence of oxygen to produce acetic acid.
- The catalyst is activated prior to use by treating it with alcohol vapor at high temperatures. During the process, the oxygen keeps the catalyst in an active condition so it can be used continuously without removal for reactivation.
- In a demonstration, 262 grams of 95% alcohol were passed through a copper oxide column at 300-340°C before the production of acetic acid peaked. The process yields high amounts of acetic
CARL HANER, OF MOYLAN, AND EDWARD P. FENIMORE, OF DIREXEL HILL PENNSYL WANIA, ASSIGNORS CORPORATION TO PUBLICKER, INC, OF PHILADELPHIA, PENNSYLVANIA, A. OF DAWARE PROCEss FOR THE MANUFACTURE OF ACETIC ACID No Drawing. Application filed August 19, 1931. Serial No. 558,188. Our invention relates to a process of pre paring acetic acid from ethyl alcohol or Itbeis oxidized well knownto that iyi ethyl alcohol vapor mixtures of ethyl alcohol and acetaldehyde, can by passin it together with oxygen over a catalyst EE and more particularly it relates to a pro as copper or silver. Difficulty has been en is cess by which acetic acid can be produced countered, however, in continuing the oxi by means of a single catalyst by the oxida dation of the tion of ethyl alcohol or mixtures of ethyl these methods,alcohol to acetic acid since in alcohol and acetaldehyde to acetic acid in amount of acetaldehydeis together there produced a large with cer the presence 10 or as air. of oxygen, either in pure form tain undesirable by-products such as acetal, One object of our invention is to provide methane, a very ester, and the like, and with but 60 small amount of acetic acid. It has a process by which substantial yields of not, heretofore, acetic acid may be obtained by the oxidation stantial yield ofbeen possible to get a sub acetic acid by the oxida of ethyl alcohol or mixtures of ethyl alcohol tion of ethyl alcohol in the presence of air 15 and acetaldehyde in the presence of oxy or pure oxygen by continuously passing the 65 gen by passing the alcohol vapor or the mix vapor ture containing acetaldehyde vapors over sible toover a catalyst; nor has it been pos pass a mixture of alcohol and acet a heated catalyst. A further object of our invention is to aldehyde continuously over a catalyst and 20 provide a process for the production of very amounts. to acetic acid in substantial 70 convert both good yields of acetic acid from ethyl al cohol or mixtures or ethyl alcohol and acet essThe for present invention contemplates a proc manufacturing acetic acid, result aldehyde, which process is characterized by ing in very good yields of acid and with but the use of a catalyst which is reactivated few by-products, by passing ethyl alcohol 25 during the process and which, therefore, can vapor or a mixture of ethyl alcohol and is be employed in the system for the produc acetaldehyde vapor over a specially pre tion of acetic acid without removal there pared non-luminous copper oxide catalyst from for the purposes of reactivation. in the presence of oxygen either in the form A further object of our invention is to of air or in pure form, the catalyst being 30 furnish a process for the catalytic produc maintained during the process at a tempera tion of acetic acid from ethyl alcohol and mixtures thereof with acetaldehyde which, ture to varying from approximately 300° C. 400°C., and preferably in the neighbor due to the reactivation of the catalyst dur hood of 320° E. C. The invention ing the process, may be run continuously, 35 any unoxidized alcohol or aldehyde pass further contemplates a process for the pro ing through the catalytic chamber being re the duction of acetic acid catalytically in which cy circulated and hence utilized in the produc out catalyst tion of acetic acid. can be used continuously with independent treatment to reactivate it, Still another object of our invention is due to the fact that the oxygen during the 40 to provide a novel catalyst for the produc process acts upon it and keeps it in an tion of acetic acid, and the method of pre active condition. The catalyst which is employed in the &C. paring it, which catalyst is capable of pro present ducing large yields of acetic acid from ethyl in any invention is activated copper oxide suitable form such as mill scale, alcohol or mixtures of ethyl alcohol and copper oxide 45 acetaldehyde in the presence of oxygen, Prior to its usewire, copper oxide gauze, etc. in the process of the present C and is capable of during the process. reactivation by the oxygen invention, it is treated to render its suitably active These and other objects will be apparent accomplishedfor the purpose. The activation is . hereinafter from a consideration of the oxide by treating the heated copper 50 specification and claims. with alcohol vapor preferably in the absence of air. At first the proportion of 2 1,911,815. alcohol changed into acetic acid is very low at the temperature desired by external but this increases as the passage of a cohol means. The products issuing from the tube vapor is increased until a maximum propor are for the most part water and acetic acid tion is obtained, thereafter the proportion vapors containing some acetaldehyde and a of alcohol converted begins to decrease. condensed little unconverted alcohol. The vapors are The treatment of the catalyst is stopped at and the alcohol or absorbed by suitable means or or near that point where the production tilled from the mixture and acetaldehyde are dis of acetic acid is at the maximum. and utilized in the In a typical case, 7 pounds 7 ounces of process. If a continuous process is desired. the products issuing O copper, oxide are placed in a tube making chamber or tube are condensed at a tem from the catalytic a column of catalyst thirty-eight inches perature below the boiling point of acetic long. Alcohol vapor is passed through the column of catalyst which is maintained at acid and above the boiling point of the ethyl alcohol and acetaldehyde, in which case sub 80 300° C. to 340°C. at the rate of 70 grams stantially 15 of 95% alcohol per hour. In this case, it is in the firstall of the acetic acid is retained found that the formation of acetic acid is aldehyde forcondenser while the alcohol and at its peak'when 262 grams of 95% alcohol condensed or absorbed inpart the most pass on and are subsequent appara have been passed through the column. It tus and are continuously added to the will be understood that the rate of passage hol delivered to the catalytic chamberalco or 85 20 of alcohol, the amount of alcohol necessary tube. Obviously, if acetaldehyde is desired and the temperature of the catalyst may all as a by-product, ethyl alcohol alone and the be varied to suit the particular conditions air or pure oxygen are passed through the existing. In carrying out the process for the manu catalyst, w and the acetic acid and acetalde 90 25 facture of the acetic acid, the catalyst is hyde formed are recovered as finished placed in a catalytic chamber which is main products. tained between 300° C. and 400° C. and In a typical case, 7 pounds 7 ounces of preferably in the neighborhood of 320° C.- copper are oxide activated as herein described placed in a tube, making a column of 95 340° C. The ethyl alcohol vapor, or the catalyst thirty-eight inches long. 109.2 liters 30 mixture of ethyl alcohol vapor and acetal of air are passed dehyde, and air or pure oxygen are pref 95% strength at 46 C. at such through ethyl alcohol of erably preheated to a temperature approx air is approximately saturateda with rate that the alcohol imating that of the chamber in order not to vapor. Water vapor substantially equalling 00 chill the catalyst and make it less active, al the alcohol vapor in weight is then 35 though this preheating step is not necessary to the alcohol vapor-laden air. Thisadded mix if the operator deems it inexpedient. The ture is passed through the activated copper amount of oxygen employed is such that there will be sufficient present in the catalytic oxide mately catalyst maintained at an approxi, constant temperature in a bath of 05 chamber not only to furnish oxygen for the liquid sodium and potassium nitrate, the 40 oxidation of at least a portion of the alcohol and acetaldehyde but also for maintaining bath temperature being kept at approxi the catalyst active. For the purpose of ob mately 325° C. by external means. The rate taining the best yield, it has been found ad 67.6 grams ofofthe95%mixed of passage gases is such that alcohol per hour are O vantageous to use such a proportion of oxy 45 gen that practically all of it will be utilized passed through the tube. From 47.4 grams in the catalytic chamber. It has also been grams of 95% alcohol, there are obtained 26.27. found that the addition of water vapor or acetaldehyde. of acetic acid and 13.57 grams of the use of alcohol of less strength, than 95% A little unchanged alcohol is also recovered. will give substantially higher yields of acetic is desired as a finished The acetaldehyde, unless it 5 50 acid than are obtained when water-free al product, together with the unconverted alcohol is mixed with the cohol or 95% alcohol is used. It has been found advantageous to pass alcohol In a fed to the catalytic chamber. typical case where both ethyl alcohol the air or pure oxygen through the alcohol and acetaldehyde in a vaporizer maintained at a proper tem 110.4 liters of freeareairfed are to the catalyst, 20 passed through 55 perature to give the ratio of alcohol of ox ygen desired. The vaporizer may also con ethyl alcohol of 95% strength containing tain acetaldehyde in which case the vapor acetaldehyde kept at a temperature of 42 laden air or oxygen contains both alcohol stantially saturateda rate C.-43° C. at such with that the air is sub alcohol and alde 25 and acetaldehyde. This vapor laden air is hyde vapor. Water vapor substantially 60 then, passed through a tube charged with equalling the combined the activated copper oxide catalyst. The cohol and acetaldehyde is then added amount of ethyl al tube which may be of metal such as iron or vapor-laden air. This mixture is passed to the copper is maintained at the desired temper through the activated copper oxide catalyst ature by any suitable means, for example, 30 65 by placing it in a liquid which is maintained arranged in a metal tube so that 7 pounds 7 1,911,315 3 ounces make a column of catalyst thirty alcohol vapors at an elevated temperature eight inches long. During the passage of until the production of acetic acid is at or the vapor-laden air, the catalytic chamber near the maximum, and thereafter condens or tube is maintained at the desired temper ing the vapors ature by placing it in a bath of a liquid 2. The processto of obtain the acetic acid. acetic acid 70 mixture of sodium and potassium nitrates catalytically which preparing heated externally to a temperature of 325 vapor, containing essentially as passing comprises an a active C-327°C. The rate of passage of the mixed ingredient a compound capable of catalytic O gases is such that a total of 60 to 70 grams oxidation to form acetic acid, and oxygen of alcohol and acetaldehyde are passed through the tube per hour. From 31.6 grams athrough a catalytic chamber maintained at 75 of 95% alcohol and 15 grams of acetalde in contact withbetween temperature a 300° C. and 400° C. catalyst of non-luminous hyde, there are obtained 23.36 grams of copper oxide, said catalyst having been acti acetic acid and 15.33 grams of acetaldehyde vated 5 with a small amount of unchanged alcohol. alcoholbyvapors treating copper oxide with ethyl 80 in the absence of oxygen The acetaldehyde and alcohol are continu at an elevated temperature until the produc ously separated from the acetic acid as here tion of acetic acid is at or near the maxi inbefore described and are continuously add mum, and thereafter condensing the vapors 20 ed to the supply of ethyl alcohol passed to obtain the acetic acid. through the catalytic tube or chamber. 3. The process of preparing acetic acid 85 In both examples, the catalyst is of such catalytically which comprises passing a a nature that it is reactivated during the vapor, containing essentially as an active in process by the oxygen passed through it, gredient a compound capable of catalytie thus a process is provided in which the oxidation to form acetic acid, and oxygen 90 catalyst can be used continuously without through a catalytic chamber maintained at the necessity of its removal and reactiva a temperature in the neighborhood of 320 tion by a separate process. The amount of C-340 C. in contact with a catalyst of air or oxygen to alcohol and aldehyde given non-luminous copper oxide, said catalyst in the preceding examples may be varied 30 widely, care being taken, however, to avoid havingwith been activated by treating copper. 95 the formation of explosive mixtures. It is oxide ethyl alcohol vapors at an ele to be noted that herein in both the specifi acetic acid is at or until vated temperature near the production of the maximum, and cation and claims the word "oxygen' in thereafter condensing the vapors to obtain 25 cludes both air and oxygen in pure form. the acetic acid. Furthermore, the strength of the ethyl al 4. The process of preparing acetic acid 100 cohol employed as well as the amount of catalytically which comprises passing a water vapor added may be varied within vapor, containing essentially as an active in considerable limits, pure 95% alcohol or pure gredient a compound capable of catalytic 40 95% alcohol and acetaldehyde being em oxidation to form acetic acid, and oxygen ployed if desired. In most instances, it is found that some water vapor is desirable, through a catalytic chamber maintained at 105 and it will be obvious that the amount em a temperature between 300° C. and 400° C. ployed determines the concentration of the in contact with a catalyst of non-luminous acetic acid solution obtained. The acetalde copper oxide, said catalyst having been acti hyde and/or water may be added to the al vated alcohol by treating copper oxide with ethyl O vapors in the absence of oxygen. cohol before vaporization and the whole at a temperature in the neighborhood of mixture vaporized by the air in one process, 300 or the acetaldehyde may be added to the was acetic acid is at or near the C-340° C. until production of the maximum. and 50 ter and the mixture vaporized separately and thereafter condensing the vapors to obtain mixed with the alcohol in air mixture. It 5 will thus be seen that the specific steps em the5. acetic acid. . . ' The process of preparing acetic acid ployed in the process are capable of wide va catalytically which comprises passing a riation without departing features of our invention. from the essential vapor, containing essentially as an active We claim: ingredient a compound capable of catalytic 1. The process of preparing acetic acid oxidation to form acetic acid, and oxygen 120 catalytically which comprises passing a through a catalytic chamber maintained at vapor, containing essentially as an active a temperature in the neighborhood of 320° C) ingredient a compound capable of catalytic C-340°C. in contact with a catalyst of non oxidation to form acetic acid, an oxygen luminous copper oxide, said catalyst having 25 through a catalytic chamber maintained at been activated by treating copper oxide with a temperature between 300° C. and 400° C. ethyl alcohol vapors in the absence of oxy in contact with a catalyst of non-luminous gen at a temperature in the neighborhood of 65 copper oxide, said catalyst having been acti 300 C-340° C. until the production of vated by treating copper oxide with ethyl acetic acid is at or near the maximum, and 30 4. 1,911,815 thereafter condensing the vapors to obtain vapor, containing essentially as an active in gredient a compound capable of catalytic the acetic acid. 6. The process of claim 1 in which water through a tocatalytic oxidation form acetic acid, and oxygen chamber maintained at yapor is passed through the catalytic cham ber with the oxygen and vapor containing a temperature in the neighborhood of 320 70 essentially as an active ingredient a com C-330°C. in contact with a catalyst of nonluminous copper oxide, said catalyst Ed capable of oxidation to form acetic having been activated by treating copper CC. 7. The process of claim 2 in which water oxide with ethyl alcohol vapors in the ab O vapor is passed through the catalytic cham sence of oxygen at a temperature in the ber with the oxygen and vapor containing neighborhood of 300° C-340° C. until the essentially as an active ingredient a com production of acetic acid is at or near the Ed capable of oxidation to form acetic maximum, condensing the vapors, separat ing the acetic acid from the unoxidized com 8CO pounds, and continuously returning said un 80 8. The process of claim 4 in which water oxidized vapor is passed through the catalytic cham compounds to the system to be re ber with the oxygen and vapor containing st.prized and re-passed through the cata essentially as an active ingredient a com y: The process of claim 10 in which pound capable of oxidation to form acetic water vapor is passed through the catalytic 85 20 acid. chamber with the oxygen and vapor con 9. The process of claim 5 in which water taining essentially as an active ingredient vapor is passed through the catalytic cham a compound ber with the oxygen and vapor containing acetic acid. capable of oxidation to form essentially as an active ingredient a com 14. The process of preparing acetic acid 9) pound capable of oxidation to form acetic catalytically which comprises passing a va acid. 10. The process of preparing acetic acid por containing essentially as an active in catalytically which comprises passing a gredient a compound capable of catalytic vapor, containing essentially as an active oxidation through a tocatalytic form acetic acidmaintained chamber and oxygenat 30 ingredient a compound capable of catalytic oxidation to form acetic acid, and oxygen aintemperature contact with between 300° C. and 400° C. a catalyst of non-luminous through a catalytic chamber maintained at a temperature between 300° C. and 400° C. copper oxide, said catalyst having been acti in contact with the catalyst of non-luminous vated by treating copper oxide with ethyl 35 copper oxide, said catalyst having been acti alcohol vapors at an elevated temperature vated by treating copper oxide with ethyl untilnear the production of acetic acid is at or the maximum, the amount ofsufficient oxygen alcohol vapors at an elevated temperature passed through the system being until the production of acetic acid is at or in amount to cause oxidation of at least a near the maximum, condensing the vapors, 105 40 separating the acetic acid from the unoxi portion of the initial ingredients and to dized compounds, and continuously return maintain the catalyst in an active condition, ing said unoxidized compounds to the sys to 15. obtain the acetic acid. The process of preparing acetic acid tem to be re-vaporized and re-passed through catalytically which comprises passing a the catalyst. vapor containing essentially as an active 10 11. The process of preparing acetic acid catalytically, which comprises passing a ingredient a compound capable of catalytic 45 oxidation to form acetic acid and oxygen vapor, containing essentially as an active in through gredient a compound capable of catalytic a temperature a catalytic chamber maintained at oxidation to form acetic acid, and oxygen C-340° C. in incontactthe neighborhood of 320° with a catalyst of 50 through a catalytic chamber maintained at a temperature in the neighborhood of 320° non-luminous copper oxide, said catalyst hav C-340° C. in contact with a catalyst of non ing been activated by treating copper oxide luminous copper oxide, said catalyst having with ethyl alcohol vapors at an elevated tem been activated by treating copper oxide with perature until the production of acetic acid is 120 5 ethyl alcohol vapors in the absence of oxy at or near the maximum, the amount of oxygen gen at an elevated temperature until the passed through the system being sufficient in production of acetic acid is at or near the amount to cause oxidation of at least a por maximum, condensing the vapors, separat tion of the initial ingredients and to main 0 ing the acetic acid from the unoxidized com pounds, and continuously returning said tain the catalyst in an active condition, and thereafter condensing the vapors to obtain. unoxidized compounds to the system to be the acetic acid. re-vaporized and re-passed through the cata 16. The process of claim 14 in which water lyst. vapor is passed through the catalytic cham 12. The process of preparing acetic acid 30 65 catalytically which comprises passing a ber with the oxygen and vapor containing es 1,911,815 sentially as an active ingredient a compound capable of oxidation to form acetic acid. 17. The process of claim 15 in which 5 water vapor is passed through the catalytic chamber with the oxygen and vapor contain ing essentially as an active ingredient a compound capable of oxidation to form ace tic acid. O CARL HANER. EDWARD P. FENIMORE.