Patented June 22, 19$4
2,681,930
UNITED STATES P/iTEHT OFFICE
2,681930
DEAN AGT*
Baymom‹d A. Frans, El &orade, Art., assignor to
Lion Oil Coz pony, Ek JOera.do, Arh., a corpora-
No Brawing. Application Only 8ï, 1q53,
Serial de. 3’f0,605
18 Cïaizns. (6t. 360—555)
This invention relates to an improved process
of proétucing urea, and more particularly to the
production où urea from carbonyl sulfide and
ammonia.
Unless otherwise specified herein, yields of urea
are given a.s per cent by weiglit and are fiased
on to) carbon dioxide or earbonyl sulfide, (b7
urea of 100 No purity, and (c) on the reaeian*s
being passed through tne reaction zones only once
ti. e. no urea resulting Jrom recycle is incliided
in *lie yields, nor is recycling necessary in the
present inventions . By “excess” and “subs*antial
excess” of ammonia as used Serein is meant that
the quantity of ammonïa involved is more than
the stoichiometric requirement. PreieraÔly the
ammonia is employed as about i0 je—30 je solu-
tion, by weight, in metlianol and at a ratio of
at leasv about tlaree mots animonia to one mol
carbonyl sulfide. “Riixture” as used Serein is
intendett to include s solution as well o.s a slu.rry.
Wnile it ïs much preferred ana contemplated
that this invention will be carried out under con-
ditions as Serein disclosed, sucé that no slu.rry
is involved during the reaetion où carbonyl sul-
fide and ammonia, it is within the scope of this
invention to dave a slurry ai this point, e. S. the
relative amount of methanol to aminonium thio-
carbamate formed could be sucé that soir.e of the
latter would not dissolve in the ir.ethanol.
One conveiitional process où manuiacturing
urea in•/olves subjecting a mixture of carbon
dioxitte and amrr.onia to an elevated pressure and
temperature. there are a ri-umber of modifica-
tions to this so-called carbon dioxide process, but
only two of thèse are in commercial use today.
de conditions vary from 180º C. anjt 3000 p. s. i.
to 210º €J. and 6000 p. s. ?. and up to 250 9o e.xcess
ammonia a.bove the stoicliiometric requirernent,
the yi•1ds of urea un-der thèse conditions varying
from 40 % to 50 No . the art states tnat v/1iile
liigher yields per pass can de obtained, ii is im-
practica.1. Altnough the carbon dioxyde process
nas been in commercial use for a numb r o:f
years, it has its drawbacks. One serious clrav -
bach is that the cost of buildinp• and operatins
the plant is vert nixh because of me liign pres-
sure requireû. An additional drawbac'z 1s tliat
the yields ai’e undesirably low.
Anoiher conventional process of producing
urea comprises subjecting a ni::iure où carbony'
sulfide and am.monia to a pressure où 300-500
p. s. i. a.net a tempero.ture o:f 110º C.—130° G. Undor
thèse conditions a.ri interine5iate product, am-
monium thiocarbarnate, form.s as a precipita.te
and is convertecl to urea. Althouah yields up
to
EÖ%BREA
P.çgroxïnaately 70Po urea arereported foi this sO-
called carbonyl sulfide process, the art has not
develop d the process beyond a very small lab-
oratory scale. Likewise on.e major diUncultv witn
flits process is the high pressure reo_uired. Be-
ce.user the ammon.ium thiocarbarnate is in a soli5
state, another ttiificulty involves handling it. A
rarities dif6culir is that at least one and prefer-
s.bly both of the reactants must be liquefied in
ord.er to accelerate the reaction.
An object or this invention is to provide an
improveti process of producing urea. é. further
object is to provide an improved process of pro-
wincing urea f rorr. carbonYl sulfide anti ammonia.
.A still further object is to overcome the draw-
'oacâ,s of the p›-ior art. Another object is to pro-
aide suer. a process by which, as compared with
the test linoivn orior arc processes, substantially
lai%lieF yr.Eds of' urea csn be produced unfier sub-
20 stantially lower conditions of pressure and tem-
perature. 'rhe above *nd oth°-r objects will be
apparel.I from th.e description of this invention
s‘ ven hereinaiter.
I nave :found b,y employing m.ethanol that the
25 o.mmoniurn thiocarbaniate dissolves therein as
last as iorm.d and thereby greatly improved the
F›rocess froin an engineering or handling stan-d-
point. Tire use of metnanol is also advantageous
in OU.er I’espects, as is disclosed hereinafter. In
aéidition I la-ave found that, as compared with the
art, a marked increase in yield of urea is ob-
tained under lower pressure and temperature.
the above objects are accomplished according
to ‘che present in'/ention broadly by reacting to-
Beth.er carbonyl sulfide and ammonia in the
iaresence of methanol, heat-'ne the resulting mix-
ture at a urea-forming temperature but below
II°-.• temperature at which urea substa.ntiallr de-
c,omiooses, and then I'emoving die methanol
Proc›e specifically the reaction desirably is car-
ried out emploxing an excess of ams.ionia, and
i› re erably the carbonyl sulfide and ammonia are
Initially in *.he gaseous state. In c* rying out
the reaction it is lil:eu ise desirable to introduce
ammonia gas into methanol and add carfionyl
sulfide to the e.mmonia-methanol mixture.
In loracticinp this invention according to a
preferred embodimen-t thereof, ammonia gas is
r.fixed with anhydrous methanol an5 with the
these.thing solution is m.ixed carbonyl sulfide gas,
th-- r-soler ratio of ammonia to carbonyl sulfide
being sweater than about 3 to 1. Thus at room
tern-perature the intermeciat•. product, am-
monia.n tiiiocarbanaate, ia iorrried. almost iristan-
•,› ianeo'as1y. T'he avr.monium thiocarbamete is
 5,081,080
4
converted to urea br subjecting in a closed sys- carbamate to urea. At the end of each run, the
temthe mixture thus formed to a temperature pressure was released from the reactor and the
of 80° C.-120° C. and the autogenous pressU.re de- methanol distilled from the mixture and recov-
veloped until the reaction 1s substantiaily com- erect for re-use. ’rhe urea was recovered from the
plete. Then the methanol is remo*/ed, •. g. by 5 distillation residue and then analyzed in order to
distillation. During the distillation of the metha- determine the yield.
nol the ammonia and sulfur values are also driven 2'obIe 2
or and may be recovered, thus leaving the urea
behind. The distillation may be continued to
the point at which urea crystallizes from solu- 10 Run Ratto M0l NOl8
NSU Time TemP., Autogonous
Pressure, Area,
tion'. or the mixture may be completely evaporated No. N£fa/ per %OUfS ° G. r
to dryness and the urea crystallized from fresh G OS Liter
methanol.
While it is preferable to operate this invention 1. . . .. 6. 64 18. 4 16 t0 25 16.7
2....... 11.8 8.1 1 60 40 76.1
under the above conditions, iv will be seen from 16 3........ 11. 8 8. 1 3 s0 •.5 s7. 7
the examples given hereinafter that conditions
outside these aFe also contemplated. The ex-
amples show the use of temperatures of 40° C.-
140° C. and a ratio of 1.84—39.o vols ammonia
peF mol of carbonyl sulfide. Also the examples
show that the invention can he practiced in an
open system, in whieh event the pressure is sub- 12- -. . . 5. 4 15. 1 0. 25 140 260 100. 0
stantially atmospheric.
Altliou n other means may be employed, the A number of advantages of the; invention are
following give good results in recovering the am- clearly shown by the data in the above examples.
2
monia and sulfur values. The escapin, gases * Ctook yields are obtained at only atmospheric
from the methanol distillation are cooled to tare- pressure and very mild temperatures even with
cipitate therefrom the ammonium bisulficle men- relatively low ratios of ammonia to carbonyl sul-
tioned below. The excess ammonia ge.s is thus ñcle, the lo•v ratios reducing the amount of am-
separated for re-use. The ammonium bisulfide monia to be recovered for re-use. In faet, prac-
is warmed and passed through sulfuric acid, ** tically theoretical yields are onta.ined under sub-
forming ammonium sulfate and allowing the hy- stantially less drastic conditions than the pressure
drogen sulfide ,•a.s to bubble on through. to and temperature disclosed in the art. £''urther-
sizlfur value then is recovered from the hydro8en more, these high yields are obtained in only a
sulfide by known methods, e. g. bx partial oxida.- single pass of the reactants through the reaction
tion thereof. ** sone.
The following examples illustrate a plt*rality of Although the present invention has been de-
specific embodiments of this invention. 9me yield scribed with ref‘erence to specific embodiments
of urea, in per cent Dy weight based on COS thereof, it will be understood by tnose skilled in
charged., was determined by the well known the art that many of the conditions appearing
Urease method. Allowance was made ror the *< hereinbefore may be varied z'ithout departing
amnaoniacs.I nitrogen, which was determined by from the spirit and scope of the invention. The
tne formaldehyde method given in A. O. A.. c., invention is readily adaptable to either a batch
seventh edition, 1950, paae 14, paragraph *.28. process, a semi-continuous process or a con-
tinuous process. While, for the safe of‘ clarity
EXAMPLE 1 and simplicity, the invention has been d••°cribed
In carrying out these runs at atmospL.eric pres- with reference to carrying out the ammonium
ture, ammonia gas was passed into a.nnydrous thiocarbamate-forming reaction at room tem-
mets.anol ann then carbonyl sulfide gas wa,s perature tabout 20° C.1 , lower or higher tempera-
mixed ir:to tire resulting solution. his portion tures can be employed. Although it would not
of the reaction, in which ammonium thiocarbam- pq appear advantageous to reduce this temperature,
rite Jorms and dissolves in the methanol as last under ceFtain circumstances one may desire to
a,s formed, was carried out at room temperature recycle the methanol and the excess ammonia at
using the quantities or inateria.1s shown in TaDle 1 a temperature Just below the boiling point of
below. the final *olution was heated at a tem- methanol.
peratui'e of about 63° C.—65° O. until substantiail Although me mechanism of the reaction ac-
all of tne methanol was distilled. be urea was cording to this invention is not definitely linown,
recovered from the distillation residue and then there is evidence to support vhe following theory
analyzed in order to determine the yield. and it is presented for what aid it may be in
TQbfe £ understanding tne invention and not as a limita-
tion thereof.
Mobs the following reactions are thought to be in-
volved.
Run Nm° per Temp., Urea,
No. Liter ° G. Pressuro 1. methanol Nil,—G O—SN£f‹
Percent
Methanol Yield sN£fi + o oa R.........,
’“ £feat
1. _.. 6. 9 3. 6 G3—6ti Ataospbcric.. 46. 4
IT. NHwG O—SNlIi —+ Njf:—G O—N£fi 1 TfiS
Methanol
2.......- 38. 0 G. 6 63—65 ..--.do..... _.. s2.
III. Hi8 -{- NSU N£fi -IS
EXAMPLE 2 Equations T and IT illustrate t,iie main reactions
In these runs, the ammoni'am tliiocarbamate 70 producing urea. trst, the intermediate mate-
intermediate was formed under the same condi- rial, ammonium thiocarbamate, is produced
tion as in Example 1 above using the quantities tEquation In and then urea and hydrogen sulfide
of materials shown in Table 2 below. The final are produced on heating (Equation III . the
solution was hea.ted in a closed vessel under the use of an excess of ammonia increases the yield
conditions shown to convert the aininoniuin thio- i> of urea. ’I’wo reasons are advanced to account
 I2,B81,830
for this. First, the excess of ammonia tends to
drive the reaction to completion and thus flavors
a hign yield of ammonium tiaiocarbamate (Equa-
tion 11 according to tne law of mass action.
Second, the excess où arnmonia tends to dri•7e the
reaction to completion by virtue or removing one'
of the products (hydrogen sulfide in Equation lil
of the reaction fv/Iaich otherwise would tend to
reverse the reaction) and thus favors a high yield
of urea.
It is believed that the use of a closed system
t autogenous pressurel in converting the am-
monium thiocarbamate to urea, as who z/n in
Equation II, further increases the yield of urea
for two reasons. First, the excess ammonia is 15
not allowed to escape the reaction zone, which
results in maintaining excess ammonia in tne
reaetor at all times. The advantage of this is
explained in the immediately preceding para-
graph. Second, increased pressure promotes Re- 20
action III which tends to make Reaction II no to
completion by virtue oJ removing one où the re-
action products therefrom.
Wrther theorizing, it is thought that meth-
anol serves four purposes. First, it serves as a 25 at about atmospheric pressure until substantially
solvent for the ammonium thiocarbamate tEqua-
tion Il . Second, it tend.s to riaimtain the epuilili-
rium in Equation III in tne form of ammoniUm
bisulfide. Third, the meihanol tends to reduce
the pressure developed while convertina the a.m- 30 anol at about room temperature and atmospheric
monium thiocarbamate to urea. Fourth, the
metlianol stabilizes the ammonium bisulfide
against decomposition.
As many apparently v/ideIy different embodi-
ments of this invention may be made witnout de- 35 methanol and excess ammonia thus evaporated.
parking from the sioirit and scope thereof, it is to
de understood that the invention is not limited
to the specific embodiments thereoi except as de-
flned in the appended claims.
This application is a Continuation in part of IO tu.re of about 63° C.—65° C. at about atmospneric
my cop=nding applications i erial No. 225,060,
bled May 7, 1951, and Serial No. 334,087, filed
January 29, 1953, both now abandoned.
what is claimed is:
1. Process of preparina urea wl2ioh comprises
reactinq together carDonYl sulflde and ammonia
in the presence of metlianol, heating the resulting
mixture at a urea-formmg temperature but be-
how the temperature at which urea substantially
decomposes, and then removing the methanol.
2. Process of preparing urea which comprises
xeacting together at about atinospherie pressuFe
and room I.•mperature carbonvl sulfide and am-
monia in the presence of methanol, heating the
resulting mixture in a. closed vessel at a urea-
ïorming temperature but below the temperature
at which urea substantially decomposes, and then
removing the methanol.
which comprises
3. Process oJ preoaring urea
reacting toget'ner carñonyl sulfide ana ammonia
in the presence of metnanol an5 then recovering
the methanol by distillation at about atmos-
pheric pressure.
4. Process of preparing urea which comprises
reacting together at atmospheric pressure ear-
bonyl sulfide and ammonia in the presence of
methanol and then recovering the methanol by
dis*illation at about atmospheric pressure.
5. Process of preparing urea which comprises
reacting together at about room temperature
carbonyl sulfide and ammonia in tire presence of
metnanol, and subjecting the resulting reaction
mixture to a temperature of about 63° C.—65° C.
at about atmospherie pressure.
6. Process of preparing urea which comprises ’/ 5
6
reacting together carbonyl sulfide and ammonia
in the presence of methanol, a substantial excess
of ammonia being emlsloyed, and then Recovering
tire methanol br distillation at about atmospheric
pressure.
7. Process of preparing urea which comprises
reacting together carbonyl sulfide gas and am-
monia gas in the presence of anhydrous methanol,
a substantial excess of ammonia aas being em-
10 laloyed, and then recovering the methanol by dis-
tillation at about atmospheric pressure.
8. Process o* preparing urea wnich comprises
reacting together at atmospheric pressure at
about room temperature carbonyl sulfide as and
mm-monia gas in the presence oJ anhrdrous meth-
anol, a substantial excess of ammonia gas b.ring
employ=d, o.nd subJecting the resulting reaction
mixture to a temperature of about G3° C.-65° C.
aL about atmospheric pressure.
9. Process of preparing urea which comprises
mixing carbonyl sulfide gas and a substantial
excess of ammonia gas with methanol at about
room temperature, and subjecting the resulting
mixture to a temperature of about 63° C.—65° C.
all of the methanol has been distilled.
10. Process of preparing urea which comprises
mixing carbonyl sulfide gas and a substantial
excess of ammonia gas with anhydrous meth-
pressure, subjecting the resulting mixture to a
temperature of about 63° C.—65° C. at about at-
:uospheric pressure until substantially all of the
methanol has laeen distilled, and recovering the
11. Process of preparing urea which comprises
mixing ammonia gas with methanol, mixin car-
loonyl sulfide gas Leith the resulting mixture, and
subject.ing the thus formed mixture to a tempera-
pressure.
12.Process of preparing urea which comprises
reacting together at about atmospheric pressure
a.nd room temperature carbonyl sulfide and. am-
monia ii;. the presence of methanol, heating the
resulting mixture in a closed vessel at a temper-
ature not in excess or about 140° C., and tnen
em.oving the methanol.
iz. rrocess où preparing urea v/hich cona.prtses r-
•actint tos•-tner at about atmosphei’ic pres- sure
nnd room tern aerature carbonyl suliiac an-d
ammonia in tt'.e presence oi methan-o1, l•.eating
the resulting n.fixture in a closed v•-ssel at a tern-
cloying the methanol.
14. Process of preparing urea which comprise.s
reacting together at about atmospheric pressure
an5 room temperature carbonyl sulfide and am-
monia in tne presence où methanol, neating the
resulting mixture in a closed vessel at a. temper-
ature oJ about 80° C.-120° C., and then remo•vine
the methanol.
15. Process of preparir-g urea which comprises
reacting together at about atmospheric sressure
and. room temperature carbonyl sulfide and arn-
monia. in the pres•nce of metiianol, the inolar
ratio of ammonia to carbonyl sulfide being at
least aborit 1.8 to i, heating the resulting iix-
tyre in a clos d vessel at a temperature no* in
excess of about UTI° C., and then removing the
methanol.
16. Process of preparing urea which comprises
reacting together at about atmospheric pressur•
and rcom temperature carbonyl sulfide and am-
monia in the presence of methanol, the molar
 5,081,830
8
ratio of ammonia to carbonyl sulfide being at in a closed vessel at a temperature of about
least e.bout 1.8 to 1, heating the resulting mix- 80° C -120° C., and then removing the methanol.
ture in a closed vessel at a temperature of about
40° C.—140° C., and then removing the methanol. Reference Cited inthefleofthW patent
17. Process of preparing ui ea v/hich comprises UNITED ZTATES PATENTS
reacting together at about atmospherie pressure
and room te.nperature carbonyl sulfide and e.m- Number Name Date
monia in the presence of methanol, the molar 1,808,465 Klemenc et aI. ----. June 2, 1931
ratio of aminonia to carbonyl sulfide being at OTHER REFERENCES
least about 1.8 to 1, heating the resulting mix- Ito Scnmidt, “Ber. deut Chem.,” vol. 101 (157'?) ,
ture in a closed vessel at a temperature or about pp. 191 and 192.
°0° C.-120° C., and then removing the methanol. I£lemenc, “Z Anorg. Allgemeine Chem.,” vol.
18. Process of preparing urea which comprises 191 (1930) , pp. 269 and 280.
reacclns togeth.•r at about atmospheric pres- Kretzschmar, “J. Prak. Chem.,” vol. 7, series
s•dre and room temperature carbonyl sulnfi• and 2 f 1873) , pp. 474-7.
‹.mmonia in the presence of methanol, the molar Marecek, “Ghemicky Obzor,” vol. 23, Dee. 1948,
ratio of ammonia to carbonyl sulfide beiii8 at pp. 210 and 219.
least about 3 to 1, heating the resulting mixture