ARTHUR C. STEVENSON, E, I. DU PONY BE NEMOURS 13 COMPANY, WILMINGTON, DEL
There have been numerom applications of the reaction o! aromatic sulfonyl chlorides with ammonia yielding specific sulfonamides. The reactions are readilg carried out ia ar aqueous system. The yields are usually good. Ttie trend in the manufacture of alkyl amines fiom alcohol and ammonia has been toward continuous vapor-phase processcs Progress has been made in controlling the proportions of the resulting primary, secondary, or tertiary amines, by the proper choice of operating conditions, the use of specific catalysts, and the recycling of undesired by-products. Olin and McKenna ( 4 1 ) report yields of ethylamine, diethylaminc, and triethj Iamine of 27.4, 45.0, and 12.8%, respectively, by the vaporphase reaction of ethanol ( 5 . 2 moles), hydrogen (46.1 moles), snd ammonia (29.6 mole-) over pelleted redured nickel catall SI A t 159" C Total yields of 91.G'% of amines in approximatelj the uanie ratio ale obtained when b u t j l alcohol is substituted foi ethg.1 alcohol. MoIar ratios in the range of 2 t o 5.5 moles o t ammonia t o 1 mole of alcohol are essential. I n the absence hydrogen, very little tertiary amine is detected, while 457, of the ammonia-fiee product is found to be butyronitrile. The Intelmediate ni bile formation has been recognized by other investigators (71j in devising a tm o-step procedure for the manufaeturr of amines--Le., dehydration to the nitrile folloq-ed by hydrogenation l o the amine. The effect of hydrogen on the nature of thi. reaction i6 clearly illustrated in Table I (&),
HE direct reaction of arnnionia wlth organic compounclt iam continued t o occupy considerable attention of research investigatois over the past several years. The recent work in this field falls roughly into five broad classifications. {I) reaction of amrncrnia with alcohols and alk3! halides, ( 2 ) reaction of ammonia wnth aldehydes and ketones, (3) reaction of ammonia w;th aromatic halides and sulfonates, (4)reaction 0 1 ammonia with olefins, and (5) reaction of ammonia wlth other miscellaneous compounds. The term. ammonoljsis is u t ~ ~ a l lunderstood y to refer t o th, reabtion of ammonia with Bn organic molecule in such a manner that the ammonia, molecule is split into --M and -NH, frag ments, arhile the ieacting molecule undergoes a double deconi position type of reactlon and is thus split into two moleculece.g., NHa -b C2H,0H -+ @&l"UHZ 4- HtO. I n some cases bolt portions of the ammonia molecule are retained by the reactirr C KH3 .+ CH,CTT,organic molecule- e.g., CHa--CH-CH:! GK2NH2. While these latter reactions, as -inell as reactions involving primary wr secondary amines instead of ammonia, are not examples of ammonolvsis in the narrow sense, they have been ineluded in this review for 1-hr purpose of presenting a more nearly cor-pleie pictule of 'ha nature and extent of th.; u n x process. The scope of this review has been Iimlted to the more practicd! applications of the ammonolysis proceijs as recorded in the paten literature and reports covering the German c h e m k d practice. Unlees otherwise stated, the $elds indicated in this paprr are based on the reaction of the substance w i ~ h smmonia or Etmicc
01
Tabfa 1.
Effect of Hydrogen om Conversion
I n Presence of Hydroqca,
REACTION OF AMMONIA WGTH ALCOHOLS AND ALKYL HALIDES Only a comparatively srnall amount of recenL work ha3 mvolved the reaction of alkyl halides with ammonia. This reaction has been applied usually in the preparation of unique or unusu~z amines. Bpence (61) reports S7v0 yields of tributoxyethoxy tthylamine by treating 1.1G moles of butox~ethoxyethylchloridt with 1.6 moles of ammonia and 1.55 moles of sodium hydroxide as a 50% solution, in the presence of approximately 0.2 mok +ach of mona- and dibutoxyetho~yethylamine. Another application (66)of the "ammonolysis" of mganic halides involves the preparation of ,~~,A;-butyldifluoroaci:ta~n~tde III 907, yield f r ~ m tetrafluororthylcne and n-%rit,y!amine.
n
+ Other applicatioiis irrcludv 2,2,2-trifiuoroethylamine (7), dkenyl amines of the allyl type (IO),and N,N'-dimethylhexamethylenediamine (56). As is illustrated in these application& the usual practice involves the use of sufficient sodium hydroxidc or else sufficient excess ammonia or alkyl amine, to function a5 an acid acceptor for the resulting halogen acid. Considerable excess (5 t o 15 moles) ammonia tends to produce predominancly primary amines (10). The reactions are usually carried out unde-i moderate temperature and pressure in aqueous medium in t batchnTise manner. Yields in the range of 80 to 90% are frrquently obtained.
Wlonobiitylamrrre Dibutylamine Tribufylamins Bu tyronitrile
24 46.9 15.2 2.6
%
I n Absence of I-rydrapcu, Y,
21.7 11.8 Trace 45
The esects of modifications of catalys? compositions and prooconditions on the yields and proportions of mono-, di-. and trialkylamines are illustrated with the folloxing examples: The use ( $ 2 ) of a granular alumina support impregnated with a hydrogenation catalyst--i.e., nickel, cobalt, or chromium-ai 300 Lo 400 C. with a molar ratio of ammonia t o butyl a!cohoI of 3.98, leads to 38~31YG conversion with yields of 50.3y0 monohut jdamine and 175% dibutylarnine, Alumina-silica-chromiurri eatalyst (23) resu!ts in slightly higher. conversi0n.r (47,370) with a higher proportion of dibutylamine-ie., & yield of 43.3% monobiatylamine and 31.GYOdibutyl2HV aminea Basic aluminum phosphate at approximate14 450" C . has been reported (18) t o lead to mono-, di-* and trimethylamines in yields of 6, 23.1, and 28.67,. By returning the mono- and trimethglarnines along with ammonia and methanol, the process ear1 he made to produce essentially dimethylamine. The use of normal a,iuminum phosphate leads to a major peerentage of monomethylamine (18). This is confirmed by Andrews and Washburne (Y), who report that aluminum phosphate catalyst at temperatures of 450' 6. catalyzes the decomposition of tertiary amines in presence of ammonia with the formation of primary and secondary amines. Apparently this effect is not FLP pronounced at lower temperatures, inasmuch as Greeiiewall (26) reports 71.5Y0 conversion with normal aluminum phosphat. 86s
IN D U S T R I A L A N D E N G I N E E n I N G C H E M I S T R Y
September 1948
at 340' C. a t 2000 pounds per square inch pressure to approui-
mately equimolar proportions of mono-, di-, and trimethylamines. Other catalysts leading to high yields of mono- and dibutylamines include vanadium oxide (24) and molybdenum oxide (25) supported on a combination of alumina and silica. Olin and Deger (37) have shown that diamylamine may be converted t o monoamylamine by the use of manganese catalyst supported on carbon at temperatures in the range of 240' to 325' C. Conversions of 33 to 36% are obtained with corresponding yields of 75 t o 90%. Approximately 10 moles of ammonia are used for each mole of amine with space velocities of 600 t o 1100 per hour. A similar treatment of tributylamine leads to 32% conversion, corresponding to 43% yields. Application of this general reaction of alcohols and ammonia to the preparation of alkylarylamines leads to 94% yields, based on aniline, of monoethylaniline from aniline and ethyl alcohol (27) and essentially theoretical yields of dimethylaniline by the vapor phase reaction of methyl alcohol and aniline over an aliimina-bauxite catalyst a t 210" C. (36). Some liquid-phase batch processes have given excellent yields in specific cases. The use of ammonium salts in aqueous medium in conjunction with, or in place of aqueous ammonia, has been used with success-e.g., Oxley and Thomas (6.2) have shown 80 t o 00% conversions of ethyl alcohol to monorthylamine a t approximately 2000 pounds per square inch at 350" C. using the molar ratios of 1:8:32 of ethyl alcohol, ammonium chloride, and water. Less than 5% of the alcohol is converted to diethylamine. Monoethanolamine has been prepared (54)in 66.2% yields in an aqueous system in the presence of ammonium carbonate, through the reaction of ethylene oxide and ammonia. The principal by-product is diethanolamine. It has been reported (20) that by adding the desired quantities of di- or monoethanolamine it is possible t o prepare mono- and triethanolamine with the exclusion of diethanolamine or di- and triethanolamine with the exclusion of monoethanolamine. German information (16) indicates that with the use of 2 moles of ethylene oxide t o 1 mole of ammonia in a 20% aqueous ammonia solution a t approximately 30" C., mono-, di-, and triethanolamine are formed in yields of 75, 10, and 5% respectively. Similarly, aryldialkylolamines may be prepared from aniline and ethylene oxide. Yields, based on aniline, of a t least 98% of phenyldiethanolamine are reported, by the reaction of 2 moles of ethylene oxide and 1 mole of aniline (89, 56). By similar procedures Senkus ( 6 7 ) shows 86% yields of N isopropyl-2-nitroisobutylamine by liquid-phase reaction of isopropylamine and 2-nitro-2-methylpropanol. ISOLATION AND
PURIFICATION
The separation and isolation of the products from amnionolysis reactions are often complicated with the formation of azeotropes during distillation. One such problem concerns the separation of trimethylamine from a crude reaction mixture consisting of a mixture of ammonia and mono-, di-, and trimethylamine. I n this system the ammonia and trimethylamine form a constant boiling mixture which prevents separation of the two components by distillation. Olin (47)has devised a procedure involving the continuous countercurrent scrubbing of the azeotrope of ammonia and trimethylamine coming from the distillation step, with a hydrocarbon solvent such as benzene, tolucne, or xylene. The ammonia is flashed from the solvent and returned as vapor t o the still for stripping additional quantities of trimethylamine. Once all the trimethylamine has been removed from the crude, the mono- and dimethylamine may be separated by conventional fractional distillation and the trimethylamine may be distilled from the hydrocarbon solvent. In this manner the three amines may be obtained in purity ranging from 96 to 99%, the principal impurity being ammonia. I n a somewhat similar procedure inCS) the separation of diisopropylamine from isopropyl alcohol
1585
(boiling point 80.5' C.) may be effected. Although these two materials form a constant boiling mixture (boiling point 79 O C.), the addition of water results in an azeotrope of water and diisopropylamine (boiling point 74" C.) which can be separated by distillation from the alcohol. Distillation of the crude amnionolysis mass undpr prpssure offers an alternative method for separating di- and trimethylamine (9)-e.g., increasing the pressure from atmospheric t o 200 pounds per square inch varies the composition of the distillate from 30% trimethylamine to 7%, thus permitting the separation of dimethylamine from the mixture. A procedure for separating triethylamino from a mixture of triethylamine, water, and ethyl alcohol has been devised by Tyerman (70). Water is fed t o the top of a distillation column which in effect holds back the ethanol by distilling over a binary mixture of 90% triethylamine and 10% water at 75" C. The triethylamine is then separated from the water by warming the solution above the critical solution temperature, separating off the concentrated upper amine layer, and redistilling. Other means of effecting a separation of mixtures of amines or amines and intermediate products include washing with water a t controlled temperatures in which two liquid phases exist (40,46, 60). Chemical reagents such as inorganic bases may be used (48)t o facilitate separation of the desired amine by removal of impurities such as aldehydes, carbamates, ketimines, et c.
REACTION OF AMMONIA WITH ALDEHYDES AND KETONES Amines may be prepared by the reaction of ammonia with aldehydes and ketones. The mechanism probably involves the formation of aldehyde-ammonia type of compounds leading to an intermediate aldimine upon dehydration. Subsequent hydrogenation yields the corresponding amine. A typical reaction is illustrated in the following equations:
a - t = O
+ NH, --+
H a - C - N -I H
I
--+
With variations in the ratio of ammonia arid ketone or aldehyde the; reaction may be used to produce primary or secondary amines. Likewise, tertiary amines may be produced by reacting the aldehyde or ketone with a secondary amine (8). Nickel is generally used as the hydrogenation catalyst with hydrogen pressures ranging from 500 t o 2000 pounds per square inch. The effect, of the ratio of ketone or aldehyde to ammonia is ilIustrated in the preparation of dibenzylamine by the reaction of benzaldehyde and ammonia. With a molar ratio of 1 mole of ammonia to 2 moles of benzaldehyde the product consists of 80'8% dibenzylamine and 16.8% monobenzylamine. When a 1 t o 1 ratio of ammonia to benzaldehyde is used, 13.6 times as much monobenzylamine as dibenzylamine is obtained-Le., approximately 90% mono- and 7% dibenzylamine (7'6). Olin and McKenna (42)have devised a procedure for the manufacture of butylamines by pumping a mixture of butyraldehyde and catalysts into a chamber controlled a t a temperature of approximately 100' C., where it comes into contact with hydrogen and ammonia. The mixture is then heated to a t least 150' C. in the presence of a hydrogenation catalyst. The molar ratio of butyraldehyde, hydrogen, and ammonia, is 1 :3 :2.4. Working up the crude product showed a 90.9% yield of mixed aminesLe., 22.7'% monobutylamine, 51.276 &butylamine, and 17% tributylamine.
1586
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Vol. 40, No. 9
COURTESY E. I . U U PoNT OE NEMOURG br C O M P A N Y
Figure 1 .
Autoclave for Liquid Phase Ammonolysis of Aromatic Halides
The use of secondary and tcrLiary as well as polyhydric alcohols as solvents in the reaction of ammonia Kith aldehydes or ketones favors the primary amines as the principal product, providing favorable ammonia, niolar ratios are used. 2.-Penianone in glycerol solution is converted to 2-aminopentane to the extent of 91% (43). Similarly, 2-butanone is converted to secbutylamine in 91% yields in the presence of sec-butyl alcohol, while only a G9.2Y0 yield is obtaincd in the absence of tho alcohol (44). Likewise, under somcv hat different condit,ions, an 85% yield of n-butyraldehyde t o monobutylarnine is obtained in the presence of glycerol (&), while a lower yield is obtained with the use of methanol as R solvcnt. To a lesser extent, t>hepresence of water has been shown ( 6 9 ) i,o improve the yield of amine prepared by the liquid-phase reaction of ketones and ammonia-e.g., the yield of monoisopropylamine is increased from 78.4 to 89.0Y0 by increasing the concentration of water in tlie reaction mass from 2.66 to 42.4Yc, based on the ketone. Nitriles in t.he presence of hydrogen and ammonia, in a t least, equal molar quantities to the nitrile, hsve been converted to the corresponding amines---e.g., caprj-lonitrile is converted continuously to a mixture of 61% mono- and 27% dioctylamine. The reaction is effected at 335” C. and 208 atmospheres over a cobalt-chromite-cadmium catalyst ( I ? ) . Clark and Wilson (8) have demonstrated the conversion of 2-ethylhexaldehyde to di-2-ethylhexylamine through a two-
step procedure involving an X3(h0 coiivri 4ori t o the intermedirt, unsaturated aldimine follon ed 1 . 3 ~catalj tic hydrogenation n i t 1 3 nickcl catalyst to the dialkylamintl in Me’, yields. Downing and Pederscn ( 1 6 ) iepor 1 niore than 90% Iields of w i i ,C’,A-’-diar yldilretimine by wactjon of a bin& mole of ethylrnii diamine with 2 molcs of hydroxyacetophenooe. Davp (13) obtains a yield of 92y0 of mono-sec-butylaminc. of 99 to 1007, purity from methyl cth>J ketone and ammonia over a copper or nickcl csialy& Ammonia pressures of 100 pouiids per square inch M ilb hydi ogcii prrsiiirrs of 1000 pountb pcr squaie inch are used. Emerson (IQ) states that slightly bavic conditions in the rcsaction of an aldehyde or ketone with ammonia in the presenco ui hydrogen and nickel catalyst favor the formal ion of dialkj 1 amines, while slightly acid condition.: favor the formation o r monoalkyl amines.
REACTION
OF AMMONIA WITH A R O M A T I C H A L I D E S
AND S U L F O N A T E S Aromatic amines have bren manufactured for a number 01 years by the reaction of aryl halides or sulfonates with ammonia. Much of the current manufacture of these materials is still being, effected through the application of thew well known techniques. The usual procedure involves the use oi aqueous ammonia under pressure; the reaction is carried out in an autoclave in a batchwise manner (Figure 1). I n some cases 110 catalyst is required,
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1948
Table II. Ammonolysis Data on Aromatic Halides
o-Nitroaniline p-Nitroaniline 4-Chloro-Z-nitroaniline 2-Chloro-4-nitroaniline
28.8 21.3 38.5 36.
12: 1 17: 1 10: 1 12: 1
225-230 237-240 205-208 230-236
6.1 5.7 7.3 8.1
hut in others the results are improved by the use of catalyst, usually cuprous salts. In the specific case of the ammonolysis of the sodium salt of anthraquinone-p-sulfonic acid, sodium chlorate is used as an oxidizing agent to convert the ammonium sulIite formed during the reaction to ammonium sulfate in order t o prevent the reduction of the reactive carbonyl groups of the anthraquinone nucleus. New applications of the general method have appeared in the past few years--e.g., Daudt and Woodward (12) report the ammonolysis of dinitro-2-chlorobenzotrifluoride leading t o replacement of the chlorine atom. The use of cuprous chloride (11) permits the reaction to proceed a t lower temperatures. Similarly, Klipstein and Hill (90) report the manufacture of '2,4-dinitroaniline from 2,4-dinitrochlorobenzene and aqueous ammonia. Recent activity in this field has been concerned with the development of continuous processes and overcoming corrosion difficulties. Information recently available from I. G. Farbenindustrie (I) includes data on continuous processes on a pilot plant scale for the ammonolysis of p-chloronitrobenzene, oc.hloronitrobenzene, 2,5-dichloronitrobenzene, and 3,5-dichloronitrobenzene. This work had been motivated by the occurrence of infrequent explosions in the operation of the batch processes. A t the time of the start of the war, development work had progressed to the design stage of a plant with a rated capacity of 50 tons per month. The reaction is carried out continuously a t 200 atmospheres pressure and at temperatures in the range of 200 O t o 240' C. The chloronitrobenzenes are charged t o a preheater (180 O C.) along with both recovered aqueous ammonia (27%) and make-up ammonia (40%)-i.c., recovered ammonia butted up with liquid ammonia. From the preheater the reaction mms passes through a reaction coil of the hairpin type (100 meters X 16 mm. in inside diameter), which is immersed in a gas-fired oil bath. A long pipe of large diameter is reported to be equally effectivefor the reaction chamber. The reaction is completed in two vertical towers jacketed with high pressure steam (4meters by 90 mm. in inside diameter) which are connected in series. The pressure in the reaction chamber is held by means of an expansion valve located immediately before the expansion chamber into which the reaction mixture is released to atmospheric pressure. The ammonia is dashed from the reaction mass in the expansion chamber which is heated to 75" to 90" C., and the ammonia is recovered and recycled. The magma consisting of finely divided nitroaniline, ammonium chloride solution, and 3% ammonia is carried from the bottom of the expansion chamber by means of an inclined eccentric screw conveyer to the run-off pipe from which it flows t,o the water cooled crystallizer. Yields in the range of 95 to 98% are reported. Although it was stated that the pilot plant coil was made of iron, hdams and Livingstone believed that it was made of a chromium (2.5%)-molybdenurn (0.5%)-tungsten (0.5%)-stecl. No corrosion is observed after 10 months' operation. Table I1 summarizes the principal operating conditions for the 4nitroanilines mentioned above. Recent advances in connection with the continuous conversion of chlorobenzene t o aniline in the presence of cuprous salts include a study of the rate of flow of the charge through a
1587
tubular autoclave in relation to the rate of reaction and corrosion of the steel vessel. Williams el al. (79) have found that corrosion increases sharply between Reynolds numbers in the range 150,000 to 250,000 and that the reaction will proceed at a satisfactory rate even though the rate of flow is only slightly greater than the rate a t which the less dense liquid separates from the more dense phase. Corrosion is reduced further by preheating the mixture of chlorobenzene and ammonia in a separate chamber t o a point just below the reaction temperature. Thus, by limiting the contact time in the preheater to approximately 1 minute, and controlling the temperature a t 180" t o 220" C.,only 10% of the reaction takes place in the preheater. The reaction is cxotherniic and it is necessary to cool the reaction mixture as soon as it enter@the reaction zone. As the cooling is accomplished through the walls of the reactor, the effect is a minimizing of the corrosion of the reactor in the region where 90% of the reaction occurs and where the contact time is appreciably greater-i.e., 38 minutes. Alternatively, the reactants may be heated separately pl-ior to introduction into the reaction zone. Ballard and Winkler ( 6 )have devised a vapor-phase conversion of isophorone (3,5,5-trimethyIcyclohexene-2-one)t o 3,5-dimethylaniline using bauxite (Porocel) as a catalyst, a t 400" t o 550" C. Molar ratios of ammonia to isophorone from 2 : l t o l O : l , with space velocities of 10 per hour, are used. The isophorone reacts to the extent of 92%, 60% of which is 3,S-dimetjhylanilineof 95% purity. Aromatic phenolic compounds constitute the principal by-products. Higher molar ratios of ammonia are found to favor the formation of amines, while lower ratios favor the formation of hydroxy compounds. The gas-phase amnionolysis of 8-naphthol t o .&naphthylamine over bauxite or activated clay is reported from Germany (2Q). Best results are obtained with a clay catalyst a t 340 " to 370' c. The product is chiefly p-naphthylamine of good quality, which contains only 3 t o 4% of p,P'-dinaphthylamine and is free from unreactcd P-naphthol. The product obtained from bauxite crtthlyst at 450' C. contains numerous by-products, and is of inferior quality. I n the past it has been understood that in the ammonolysis of aryl halides, the by-product ammonium chloride was largely responsible for the general corrosive properties of the reaction mass. It was believed also that the ammonium chloride reduced the activity of the catalyst presumably by precipitating a cuprous salt as a scale on the walls of the reactor. I n order. to overcome the corrosion difficulty and to maintain a satisfactory reaction rate it was the usual practice t o feed additional cuprous salts and to recover the copper salt from the spent ammonium chloride solution by precipitation with sodium hydroxide. Williams et al. (74)have shown that this corrosion problem can be largely overcome by saturating the ammonium chloride catalyst solution with ammonia prior to recycling t o the preheater. Moreover, it was learned that any scale due t o catalyst deposition on the walls of the vessel may be quickly removed from t h e prcheater by recycling aqueous ammonia-ammonium chloride s d u tion while withdrawing a portion of the aqueous recycling layer as a purge. Contrary t o accepted belief, no adverse effect of ammonium chloride on the catalyst activity is observed. Slagh (69)reports tlhat the amount of corrosion can be reduced and the catalytic activity of cuprous salts may be maintained by preventing deposition on the walls of the reactor with the use of 0.08 t o 0.25 mole of the oxides of calcium, tin, lead, arsenic, or antimony, per mole of aryl halides. No appreciable hydrolysis of the aryl halide or amine is observed with the use of 0.01 t o 0.08 mole of these oxides and in some cases the corrosion is arrested almost completely.
REACTION OF AMMONIA WITH OLEFINS A number of recent patents deal with 1he preparation of amincs, amides, and nitriles by tho vapor-phase reaction of olefins with
x 588
INDUSTRIAL AND ENGINEERING CHEMISTRY
arm~onia. This work involves the use of comparatively purc. olefinic hydrocarbons as well as petroleum cuts containing considerable proportions of saturated hydrocarbons. The reaction i s not straightformard a n d consequently the yields are iow compared t o other ammonolysis reactions. The desired reaction i s accompanied with a certain amount ol cracking of the product aminc, particularly at temperatures in excess of 600" F. (89). Polymerization, Tvhich increases with contact Lime and tsmperature, also occurs. A third aide reaction involves dehydrogenzLtion of the aminc, liberating hydrogen which in turn con.vcrts unreacted olefin t o t~hecorresponding paraffin. While high teniroerai ures favor this reaction, it is repressed with pressures in :'xceRs of 1000 pounds per square inch. Tcter ( E & ) has devised .a continuous vapor-phase process involving the use of a cobalt catalyst support,ed on silica. The reaction is cari~iedout. at 55Q F. and 2000 pounds per square inch pressure. The reactants are prehea.ted t o 550" F. prior t o chai'gEng t,o the rract,ion zone of a fixed bed catalyst system. Liqyid ammonia and liquid dodecene are fed to tho catalyst chamber at the rates of 40 and 200 iiiL per hour, respectively. Tlir oorresponding liquid space vel.ocity is 0.2 per hour. Analysis of ilic product shows IOyo of ihc olefin charged i s converted to wganic nitrogen conkining compounds, 44% is recovered, 99; cracked, 18% hydrogcnated, and 197; pol.ymerized. While t h e aompositioa of the nitrogen containing compounds is not, given, Opgar arid Teter (60) have shown that with similar conditione a 22.6% yield of organic nitrogen coinpounds consists of I%, oct,onitrile, ZOyo primary laurylamine and lauronitrile, and 1.55T dilaurylarnine. A n alternate iiquid-phase process (63) makes use of 200-mesh cobalt catalyst suspended in the reaction mass. The reaction is effected under approximately the same conditions rn described for the vapor-phase process. This method is reporkd to lead to improved cataly8t life, sts well as.less polymerimtion, dcliydrogenation, and hydrogenation. Propionit,ri!e may be prepared from a,rnnionia and propylene v i t ~ l rmolar ratios of 4 or 5 t,o f ai 700" F. arid a t 3000 pour;ds per squai'c inch piessure. Tetw (69) reports that the reaction is %20Toas cffective at, 700' F. as at 550" F. Yields of 30 to 407, propionitrile and 40 t o 50% equiniolar mixtu ce of butyronitrilk: arid acetonitrile are obtained. Apparently the reaction i s accompanied with some carbon to carbon fission. More rccently Teter (67') shows improved yields in orga,r~ic nitrogen compounds when using olefins diluted with saturated hydrocarbons. Such mixtures are available from cracking operations. Thcj- contain 40 t o 457; propylene and 50 t o 55'3 propane and a smaller amount of etha.ne. This mnterial has been used with considera.ble excess ammonia---Le., molar ratios of 10 to 1 , over a cobalt catalyst at 600" t o 700" F. at 1500 pounds per square inch pressurc and with space velocities of 0.104 per hour. Rlany of t,he undesirable side reactions are repressed and yields based on the olefin charged are considerably improved. Organic nitrogen containing products amount t o 28.07% of t h e filefin charged. Analysis of this material indicates yields of 4.7870 acetonitrile, 12.97%, propionit,rile, 5.65c% butyronitrile, 4.61 heavier nitrilcs, and 5597$ polymeric material, Alt,hough the usual cat,alyst for this operation is coba,lt, which niakcs up approximatelj- 507; of thc finished catalyst, modifications 01 this cat,alyst lead t o deeirable effects. Tcter (66) reports a more specific catalyst with t,he addition of 1:G manganese oxide. Cracking products are reported t o be decreased, carbon deposit, is substantially reduced, L ~ mtaiyst O life is extended, and the spent catalyst is more easi1.i. removed from the reactor, It i s aJso stated that the catalyst may be regeneratcd KT. hydrogenation at 650' t,o 725" F. (68). The presence of small amounts of water---e.g., 0.25 to 0.93 mole per mole of oIefin--leads t o the formation of amides amountg to as much as 6yc of thc olefin charged, or approximately 2yoof that consumed, as conipltired t u little or no amide obtained in the a,bsencc of wateJ~ (64). ilfore recent,l.p ( 6 8 ) it has been O
r0
Vol. 40, No. 9
reported that with minor amounts of water, preferably in ihi> range of 1 % based on the total feed of ammonia, olcfin, and othcr gases, therc is an improvement in the yield of the nitrile and appreeiably less polymer format,ion. Qlin and Deger (38) have devised a modified process for the manufacture of amines by a.dding carbon monoxide or carbon dioxi.de t o the reaction mixture of olefin, hydrogen, and ammonia. As a result, the product, amine contains one more carbon atom ?han the star ting olefiri. A hydrogenation-dehydrogpnation catalyst---e.$,, zinc chroma1:e-manganese phosphate support,erl on activated carbon, or pelleted chromate-manganese oxide eatxiysl----is med. Approximately 10 m of carbon morioxiclc or carbon dioxide arc used for each mole of olefin. T i e reaction fs carried out at 350" to 370" C. under 8000 pound.s per square inch pressure with space veloc,ities of approximatolg 2,500 pc:r hour (ca!culated a t K T . P e ) through the fixed bed. Olia and Deger siate (39) f,hat by eliminating hydrogcn &om the reaction mixture Iho intermediafe amide compound niay be obtikincd. A coirlinuous process (68)for t,lre manufacture or amines has been developed which involves the reaction of an olefin an? ammonla in liquid ammonia in the presence of a, cobalt or nicltel catalyst suspended in the fluid reacticn mass. Provision is made for withdrawing catslyst from the continuously recycling system, regenerating by hydrogcna.tion at high temperaturc, and rcturriing the activated catalyst to thc system. An earlier liquidphase batdl process (51) is ba.sed on the rea,ct,ionof ethylene arid ammonium chloride at, 31 5 O @. and 120 atmospheres of pressure. A molar ratio of 16 moles of ammonium chloride to I. mole ol ethylene is used. Approximately 50% of the ethylenc chargi:d i s converted to monoethylamiae ivit,h a, corresponding convwsiorr OF 2 t o 4% to diethy1mninc,
REACTION OF AMMONIA WITH OTHER MISCELLANEOUS COMPOUNDS Sevmal proccsEes devised for the manufacture of misccllaneou~ nitriles start with mat,eria,ls other than olefins. An outstanding example i s disclosed in the recent announcement of a catalytic method for the manufacture of benzonitrilc from toluene anti ammonia (6). Wagner ( 7 2 ) reports a continuous vapo~-phmc. process for manufacturing unsaturated nitriles by passing 3 mixture of an aldehyde and ammonia a t 900" to 1300" F. over a fixed bed hpdrogena.tion-r'el)y~rogenationcatalyst.- e.g., chromic oxide supported on alumina. It is desirable t o uec ammonia molar ratios of 5 t o 1, ~ r e s ~ u rin e sthe range of 6 t o 8 atmospheres, and space velocitics of appravimately 1800 per hour. Good yields of acr) lonilrile from propionnldchyde and w-niethylacrylonitrile from isobutyraldehyrle are reported. Adiponitrile has been made (R1) from the corresponding acid by blowing thp molten acid at 200" t o 230" C~ with ammonia in the presence of 2 to 5'3, phosphoric acid or esters of phosphoric acid. The i-caction stops a t the et.mide stage if the temperat,ure is limited to 100" C. and the catalyst is omitted, Similarly, petroleum acid nitriles may be made ($8)by the reaction of ammonia and petroleum acids at 350' C. in contact, with silica, gel or ahimino,..i,h.orium oxide catalyst. A comparatively new one-step continuous vapor phase proceso for the manufacture of alkyl amines from the corresponding acids had been worked out by I. 6. Farbenindustrie (68; a t about the time of the last war. Nickel sulfide-molybdenum :sulfide is used as the catalyst. The aliphatic acid, liquid ammonia, and hydrogen are preheated t o 120" C . and then puniped into a loa-er section of a reaction cha,m.ber maintained at 200 to 250 ahosphercs. The vapors pass up through the fixed catalyst bed, which is maintsined a t 300" t o 330" C., at a liquid space velocity of approximately 0.3 per hour. The resulting mixture of alkyl. amines is separated by conventional distillation. Yields in the range of 90 t,o 92% in t,he case of stearylarnine are obtained. The reactor, having zt capacity of 10 tons per month., was 200 mm. by 5 meters high-
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1948
Potts (53) reports a similar procedure for preparing nitriles from fatty acid esters over an aluminum oxide dehydrogenation catalg st. o-Phthalonitrile has been manufactured commercially for some time by a vapor-phase reaction of ammonia and phthalic anhydride. Molar ratios in the range of 10 to 15 moles of ammonia t o 1 mole of phthalic anhydride, with space velocities of 580 per hour, are used with tungsten oxide, chromium oxide, or vanadium oxide catalysts a t approximately 400' C. Yields of o-phthalonitrile are in the range of 61.9 t o 72%, principal byproducts being phthalimide (18.9%) and benzonitrile (5.1%) (16). German information ( 4 ) has revealed a semicontinuous process for manufacturing o-phthalonitrile using a molar ratio of 80 to L of ammonia to phthalic anhydride over a bauxite catalyst. After the products of the reaction are separated out the ammonia is recycled. A yieId of 91% of theory is reported. Similar applications of this type of reaction are found in ammonolysis of glutaramide a t 320" to 400" resulting in 90% yields of the glutaronitrile (34) and in the reaction of e-aminw caprolactam (2-oxohexamethyleneimine) with excess ammonia a t 360" C. over a copper-silica catalyst ($1). The product consists of a 25% yield of e-minocapronitrile, the remainder being unchanged starting material. Hydrogenation of the nitrile in the presence of ammonia leads to hexamethylenediamine.
c.,
LITERATURE CITED Adams, D. A. W., and Livingstone, A. Y . , B I O S Final Rept. 1147,Item 22, British Intelligence Objectives Sub-Committee, London. Andrews, C. E., and Spence, L. U. (to Rohm & Haas Go.), U. S. Patent 2,153,405 (April 4, 1939). Andrews, C. E., and Washburne, R. N. (to Rohm & Haas Co.), U. S. Patent 2,095,786 (Oct. 12,1937). Andrews, D. B., et al., U. S. Dept. Commerce, F I A T Final Rept. 1313, P B 85,172, 430 (1948). Anon., Chemistru & I n d u s t r y , 61, 438 (1947). Ballard, S. A,, and Winkler, D. E. (to Shell Development Co.), U. S.Patent 2,413,598 (Dec. 31, 1946). Benning, A. F., and Park, J. D. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,348,321 (May 9. 1944). Christ, B. (to I. G . Farbenindustrie), U. S. Patent 2,170.746 (Aug. 22, 1939). Clark, J. W., and Wilson, A. L. (to Carbide & Carbon Chemicals Corp.), U. S. Patent 2,319,848 (May 25, 1943). Converse, W. (to Shell Development Co.), U. 5.Patent 2,216,548 (Oct. 1,1940). Daudt, H., and Woodward, H . E. (to E. I. du Pont de Nemoura & Co.), U. S. Patent 2,194,926 (March 26, 1940). Ibid., 2,212,825 (Aug. 27, 1940). Davy, L. G. (to Eastman Kodak Co.), U. S. Patent 2,312,746 (March 2,1943). Deen, A. G., and Lasier, W. A. (to E. I. du Pont de Nemours & Co.). U. S. Patent 2,203,861 (June 11, 1940). Dennis, N., B I O S Final Rept. 1059, Item 22, p. 52 (June 20, 1947). Downing, F. B., and Pedersen, C. J. (to E. I. du Pont de Nemours & Go.), U. S. Patent 2,301,861 (Nov. 10, 1942). du Pont de Nemours & Co., E. I., British Patent 526,497 (Sept. 19,1940x. du Pont de Nemours & Co., E. I., and Arnold, H.R., British Patent 528,987 (Nov. 12, 1940). Emerson, W. S., U. S. Patent 2,380,420(July 31,1945). Ferrer, P., B u l l . SOC. chim. belg., 56, 349-68 (1947). Fluchaire, M. L. A., and Iavorsky, S. (to Soci6t6 Rh8ne-Poulenc), U. S. Patent 2,273,633 (Feb. 17, 1942). Goshorn, R. H. (to Sharples Chemicals, Inc.), U. S. Patent 2,349,222 (May 16, 1944). Ibid., 2,389,500 (Nov. 20, 1945). Ibid.,2,394,515 (Feb. 5,1946) Ibid., 2,394,616 (Feb. 5,1946). Greenewalt, C. H. (to E. I. du Pont de Nemours & Co.), Ti. 8. Patent 2,098,289 (Nov. 9, 1937). ~
1589
(27) Hill, A. G., and Sayre, R. E. (to American Cyanamid Co.), U. S. Patent 2,377,233(May29,1945). (28) Jolly, S. E. (to Sun Oil Co.), U. S. Patent 2,295,406 (Sept. 8, 1942). (29) Kaupp, U. 8 . Dept'. Commerce, Office of Technical Servicer, PB Rept. 622 (1941). (30) Klipstein, K. H., and Hill, A. G . (to American Cyanamid Co.) , U. S. Patent 2,305,573 (Dec. 15, 1942). (31) Lazier, W. A., and Rigby, G . W. (to E. I. du Pont de Nemours t Co.). U. S. Patent 2.234.566 (March 11. 1941). (32) Liechner, H. Z., and Kesler, M.'L. (to AmericanCyanraniid Co.), U. 5. Patent 2,432,023 (Dec. 2, 1947). (33) McKenna, J. F. (to Sharples Chemicals, Inc.), U. S. Patent 2,348,783 (May 9,1944). (34) Manchen, U. S. Dept. Commerce, Office of Technical Services, PB Repl. 616 (1946). (35) Martin, E. L. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,334,782 (Nov. 23,1943). (36) Maxted, E. B., British Patent 577,901 (June 5 , 1946). (37) Olin, J. F., and Deger, T. E. (to Sharples Solvents Coip.), U. 8. Patent 2,192,623 (March 5, 1940). (38) Zbid., 2,422,631 (June 17,1947). (39) Ibid., 2,422,632 (June 17,1947). (40) O h , J. F., and Hinds, G . E. (to Sharples Solvents Corp.), U. S. Patent 2,237,628 (April 8 , 1941). (41) Olin, J. I?., and McKenna, J. F. (to Sharples Chemicals, Inc.) U. S. Patent 2,365,721(Dec. 26,1944) (42) Zbid., 2,367,366 (Jan. 16, 1945). (43) Olin, J. F., and Schwoegler, E. J. (to Sharples Chemicals, Inc.) U. S. Patent 2,278,372 (March 31, 1942). (44) Ibid., 2,278,373 (March 31, 1942), (45) Zbid., 2,373,705 (April 17, 1945). (46) Zbid.. 2.377.511 (June 5. 1945). (47) Zbid.; 2;388;217 (Oct. 30, 1946). (48) Ibid., 2,411,802 (Nov. 28, 1946). (49) O'Loughlin, W. K. (to Commercial Solvents Corp.), U. S. Patent 2,422,743(June 24,1947). (50) Opgar, F. A., and Teter, J. W. (to Sinclair Refining Co.), U. 8. Patent 2,381,709 (Aug. 7, 1945). (51) Oxley, H. F., and Thomas, E. B., British Patent 502,737 (March 23,1939). (52) Oxley, H.F., and Thomas, E. B. (to Celanese Corp. of America), U. S. Patent 2,226,635 (Dec. 81, 1940). (53) Potts, R. H. (to Armour & Co.), U. S. Patent2,414,393 (Jan, 14, 1947). (54)-Reynhart, A. F. A. (to Shell Development Co.), U. So Patent 2,186,392 (Jan. 9,1940) (55) Rigby, 6.W., and Schroeder, H. E. (to E. I. du Pont de Nernours & Go.), U. 8. Patent 2,409,315 (Oct. 15, 1946). (56) Riark, R. G. (to Carbide and Carbon Chemicals Corp.), U. S. Patent 2.275.470 (March 10.1942). (57) Senkus, M . (to Commercial Solvents Corp.), U. 8. Patent 2,419,506 (April 22.1947). (58) Sheely, M . L.,B I O S Misc. Rept. 22 (1945). (59) Slagh, H. R. (to Dow Chemical Co.), U. S. Patent 2,391,848 (Dec. 25, 1945). (60) Spence, L. U. (to Rohm & Haas Co.), U. S. Patent 2,206,586 (July 2,1940). (61) Ibid., 2,355,337 (Aug. 8, 1944). (62) Teter, J. W. (to Sinclair Refining Go.). U. 8. Patent 2,381,470 (Aug. 7,1946). (63) [bid., 2,381,471 (Aug.7,1945.) (64) Ihid., 2,381,472 (Aug. 7, 1945). (65) Ibid., 2,381,473 (Aug. 7, 1945). (66) Ihid., 2,397,705 (April 2, 1946). (67) Ibid., 2,417,892 (March 25, 1947). (68) Ibid., 2,417,893 (March 25, 1947). (69) Ibid., 2,418,562 (April 8, 1947), (70) Tyerman, W. (to Imperial Chemical Industries, Ltd.), British Patent 590,713 (July 25, 1947). (71) Usines dc Melle, British Patent 586,470 (March 20, 1947). (72) Wagner, C. R. (to Phillips Petroleum Co.), U, S. Patent 2,412,437 (Dec. 10,1946). (73) Williams, W. H., Holmes, R. D., and Fruehauf, €1. F. (to DOW Chemical Co.), U. S. Patent 2,432,551 (Dec. 16, 1947). (74) Williams, W. H., Holmes, R. D., and Widiger, A. €Jr. I.(to , Dow Chemical Co.), U. S. Patent 2,432,552 (Dee. 16, 1947). (75) Winaus, C. F. (to Wing Foot Corp.), U. S. Patent 2,217,630 (Oct. 8,1940). a
I
R ~ C E W June ED
15, 1948. Contribution 7 3 from Jackson Laboratory, E. 1. d u Pont d e Nemours & Company.
