Патент USA US2109004код для вставки
Feb. 22, 1938. ‘ F. M. ARCHIBALD Er AL 2,109,004 SECONDARY ALCOHOL PRODUCTION 1 Filed Aug-12, 195a \ I HYDROCARBON OUTLET ‘ 23 (-9 - _ § ACID 072 WATER ly/ILET Ricrcmt ACAD- L/NE_/ ' I l5;\ ‘ OLEFIN ’ OUTLET I ETHER OUTLET OLEFIN .BxsAiE/wq‘ fix/0120:4230” ’ INLET @ ' 25c vcus . A c 1.0 (.avs Patented Feb. 22, 1938 I I UNITED ‘STATES PATENT OFFICE 2,109,004 } _ SECONDARY iiLoonoL PRODUCTION Francis M. Archibald, Elizabeth, and Helmuth G. Schneider, Roselle, N. J., assignors to Standard Alcohol Company Application August 12,1936, Serial No. 95,578 v '7 Claims. (Cl. 260-156) This invention relates to an improved process carry out the process of the invention andindi for producing an alcohol directly from an ole?n oates the ?ow of materials. and relates more particularly to a catalytic process for producing an alcohol from an ole?n 5 containing two to ?ve carbon atoms. It may likewise be used to produce alcohol from an ole- ‘ ' Referring to the drawing, numeral | repre sents an absorption .tower. This tower is pro vided with acid plates 2 or other means whereby 5 good contact of the catalytic material and the ?n containing up to seven carbon atoms or more, . ole?nic material is obtained. The catalytic It is known that ole?ns may be reacted with catalytic materials to form reactive acid liquors, 10 the reactive acid liquors diluted, hydrolyzed and distilled to obtain alcohols. The catalytic material generally used is sulfuric acid, though other catalytic materials have been used, for example, material preferably used according to this in vention is an aqueous solution of sulfuric acid of 50 to 70% concentration when propylene is 10 the ole?n being reaoted- Higher concentrations of aqueous sulfuric acid up to 84% and lower concentrations to 1% may be used with propylene . phosphDriC acid, hydrochloric acid, acetic acm l5 and other acids, and also aqueous solution of salts such as zinc chloride, aluminum chloride, etc., of the concentrations at which they are capable of forming reactive acid liquors. and the other ole?ns. While aqueous sulfuric aeidisthe preferred Catalyst. other aqueous solu- 15 tions of catalytic material may be used, for 6X ample, aqueous solutions of phosphoric acid, hy It has been found that ole?ns on reacting with 20 catalytic materials of de?nite concentration and etc. It is not necessary to use the diluted sulfuric acid as such in'the absorption tower as reactive 20 temperatures form alkyl sulfates, alcohols and ethers directly. It has been shown in c'opending application, Serial No. 83,894, “Production of ethers directly from ole?ns", ?led June 6, 1936, 25 by H. G. Schneider, that after certain amounts of alkyl sulfates, alcohols and ethers are formed, the reaction reaches an equilibrium, If the ,ethers thereby produced are removed and the amount of others in the acid solutions maintained 30 at low concentration, the equilibrium is disturbed. Substantially all of the oleiins thereafter passed into the ole?n acid liquor are converted into ethers if .the ethers are removed continuously as they are formed, 35 According to this invention, it has been found that alcohol is formed directly when an ole?n is contacted with an aqueous hydrating catalyst of ammtehcncentmtion, and at, certain temperatures and pressures, and after the alcohol is sepa40' rated from the catalytic material the catalytic material reacts with more of the ole?n added to - form more alcohols. Ether is also formed which may be Separated from the catalytic material to_ gether with the alcohol. The preferred method 45 of separating the alcohol or a mixture of- alcohol _ and ether from the catalytic material is by steam stripping o?t.without th damthough f they mayS be 1 distilled t 6 a on 0 Steam‘ 0 V9“ extrac 1011 may 50 also beLuSBd- » , The invention will be more fully understood on drochloric acid, zinc chloride, aluminum chloride, acid liquor diluted to below 84%, preferably about 50% to 70%, may be used- The aqueous catalytic material is maintained at substantially the same concentration throughout the process. _ The ole?n, or mixture of ole?nS, if mixture of 2 di?'erent» alcohols is ‘to be made, substantially pure or in a hydrocarbon mixture containing the desired ole?n OI‘ OlB?IlS, lS'péiSSBd into the‘bottom of absorption tower l by means of pipe 3- This ole?n is passed into the bottom of the absorption 30 tower I under a partial pressure of the ole?n of at least 2 Pounds per square inch- Pressures of 40 to 200 01' more pounds Del‘ Square inch Par tlal pressure of the ole?n are preferred though higher and lower pressures may be used. It is 35 not necessary that the ole?n be in Vapor Phase as Ole?n in the liquid Phase may also be used to produce alcohol according to this invention. The ole?n passes upwardly through the ab sorption tOWeT I through the aqueous Sulfuric 40 acid layers on the acid plates 2- on layers may be maintained on the top of the aqueous catalytic acid layers if desired in order to obtain better con tact of. the mild and the ole?n‘ An outlet pipe a prmflded wlth 5 removes.the unrefacted materials. The valve aqueous catalytic material is 45 passed/into the abior tion tower l thmu h i - ° downward p g pab pe 6 and while flowing through the sorption tower is contacted with the ole?n mate rial. The aqueous catalytic material with the 50 reaction products in solution is passed ‘ through" reading the following description with reference pipe 1 into the Stripping tower a, The absorption to the accompanying drawingThe drawing shows a diagrammatic view in tower is maintained at a temperature of 30° C. ' or higher by means of coil 9 or other heat con 55 sectional elevation of an apparatus adapted to trolling means. The preferred temperature when 55 2 2, 1 09,004 isopropyl alcohol is being produced is about 80° inherent novelty as to 130° C. ‘ By the use of these temperatures, permits. pressures, ‘and catalytic concentration all of the We claim: ole?ns present are reacted in one pass. _ ' distilling temperature of the alcohol and ether and the concentration of the acid controlled. 10 The vapors of ‘alcohol and ether are removed through outlet I‘! and fractionated in tower is if desired, condensed and passed to storage. ‘ at the same time avoiding any dilution or con centration of the sulfuric acid so that it is of 15 absorption tower i, by means of pipe 3 though both alcohol and ether may be passed to storage. The separated sulfuric acid in stripping tower 8. is withdrawn through line it and passed ‘by means of pump l8 into pipe 6 and thereby into v spray outlet is not used to remove the alcohol and ether and at the same time to maintain the acid at the desired concentration; water is added to the acid as it enters pipe 5 before it is re-' . of the alcohol and ether that-are in solution and The separated ether is preferably recycled back into the ole?n material that is passed into the when the open steam a 1. A process for manufacturing an alcohol from an ole?n which comprises contacting an ole?n with an aqueous solution of sulfuric acid, of 1% to 84% concentration and under a partial initial pressure of the ole?n above 2 lbs. per square inch, and a hydration temperature above 30‘? 0., sep arating the aqueous solution of sulfuric acid, .10 stripping the aqueous solution by means of steam Stripping tower 8 is provided with a. steam coil in and also an open steam spray outlet H, whereby the temperature may be raised to the 20 the absorption tower i. bmadlyasthepnorart constant concentration and recontacting the residual aqueous solution of sulfuric acid of 1 to 84% concentration with another portion of the 15 ole?n to further manufacture more of the alcohol. 2. A process for manufacturing isopropyl alco hol from propylene according to claim 1, in which the ether is recirculated with the aqueous solu tion of sulfuric acid. - 3. A process for manufacturing isopropyl al cohol from propylene which comprises continu 2.5 turned to the absorption tower i through pipe ously passing propylene countercurrently to an i3 provided with valve M. The acid is used con aqueous solution of sulfuric acid of about 50 to tinuously, being recycled to the absorption tower 70% concentration whereby a substantial amount ' after the alcohol and ether are stripped out, of isopropyl alcohol is formed directly and is in 30. though it may be necessary to add small amounts solution in the aqueous solution of sulfuric acid, of the acid and water through pipe is provided continuously withdrawing the aqueous sulfuric 30 with valve ill to maintain the desired volume due acid with the isopropyl alcohol in solution, con to slight losses, and also to maintain the desired tinuously separating the isopropyl alcohol from ‘ concentration. the aqueous sulfuric acid while maintaining the The following table shows the yields of iso aqueous sulfuric acid at the same concentration propyl alcohol and isopropyl ether obtained on of about 50 to 70% and continuously recycling reacting propylene and aqueous sulfuric acid of the aqueous sulfuric acid countercurrently with different concentrations and at different temper atures and pressure over various lengths of time: 40 , 0 oncen- tration of sulfuric. ‘ my“ 0!, _ Tem mm ' " ' " Pam“! Tim9 pressure 01 pro- 9°?‘ d used .' Wax acid, .45 _ Products per 8mm lgs. ' mtg-l0ofaciii-Ill‘ of cone ylene, ' -‘ - ‘ “1 o alcohol other ' a. A‘ process for manufacturing isopropyl al- - cohol from propylene according to claim 3 in which pressure of 40 to 269 pounds per square inch and temperature of 60“ to 130° 6. are main tained. tact rh hours M01 of Mel. . more of the propylene. . 5. A process for manufacturing an alcohol from an ole?n comprising contacting an ole?n with an acid liquor that had been prepared by contacting 45 an ole?n with concentrated sulfuric acid and di Percent .50 55 f 60 ° 0. _ 55 Oil present.-..- 110 . 190 1 4 1. 37 0. 193 55 Oil present--_. 110 ' 190 2 1. 51 0.311 65 Oil present-.... 110 190 4% 1. 79 0. B8 60 60 60 Oil present... Oil present--Oil present.... 100 100 100 190 191) 190 1_ . 4% 1.54 1. 73 1. 96 0.191 0. 343 0. 670 60 60 No oil present. No 011 present. 100 ' 100 ._ 190 ‘100 4% 1. l5 1. 94 0. 150 0. 72 60 60 60 60 Oil present---Oil present._.Oil present.... Oil present..- 90' 90 90 100 170 170 170 90 2 4% 1. 42 1. 716 1. 986 1. 110 0. 088 0. 204 0. 32¢ 0. 115 60 Oil present._..- 100 60 70 70 01] present._.__ Oil present._-_ Oil present.-.- 100 100 100 90 - 90 190 100 1 2 1. 330 0:218 4}‘ .1. 390 1. 670 1. 600 0. 286 0. 463 0. 575 Alternately a second absorption tower may be provided into which the ether and oleflns sep may be used in this absorption tower. The set urated acid from the?rst absorption tower may 65 be used that is by being passed in countercurrent relation to the ether and ole?n to obtain super saturated solution. 70 . _ . The foregoing description is merely illustrative and various changes and alternative arrange ments may be made. It is not the intention to limit the process to the exact temperatures, pres sures and acid concentrations that are given but ' to limit it within the scope of the appended 75 claims, in which it is my intention to claim all iuted to a concentration less than ‘29%, whereby an alkyl ester,v alcohol and ether are formed di rectly, separating the alcohol from the aqueous solution of the hydrating catalyst while substan tially maintaining the concentra‘don of the hy drating catalyst constant and contacting more of the ole?n with the aqueous solution of the hy drating catalyst.v 6. A process for manufacturing an alcohol from 55 an ole?n which comprises passing a mixture of hydrocarbons containing clenns in counter-cur rent relation to an aqueous solution of sulfuric acid of less than 70% concentration whereby sub stantially complete removal of the ole?n from the hydrocarbon mixture is obtained and an alkyl' - ester, alcohol and ether are formed directly, sep arating the alcohol, ether and an ole?n from the aqueous solution of sulfuric acid while maintain- " ing the concentration of the sulfuric acid sub stantially constant and contacting ‘more of the hydrocarbon mixture containing olefin together with the said ether and olefin that had been sep arated with the‘ aqueous solution of sulfuric acid to form alcohols. ‘ v 7. A process for manufacturing an alcohol from 70 an ole?n which comprises contacting an olefin together with oil with an aqueous solution of sulfuric acid of 1% to 84% concentration and under a partial initial pressure of the olefin above Yrs escapee 2 lbs. per square inch, and a hydration tember ature above 30° 0., separating the aqueous solu tion of sulfuric acid, stripping the aqueous solu tion by means of steam of the alcohol and other ' recontacting the residual aqueous solution of sui furic acid of 1 to 84% concentration with an other portion of the ole?n to further manufacture more of the alcohoL- ' - - that are in solution and. at the same time avoid ing any dilution or concentration of the'sulfuric acid so that it is of constant concentration and. 3 CIS M. ARCHIBAID, Zt-il; ‘ ' - G. SCHNEIDER.