INVESTIGATION OF THE CATALYTIC OXIDATION OF AMONIA

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000200120018-8
• Release Decision: RIPPUB
• Original Classification: R
• Document Page Count: 24
• Document Creation Date: January 4, 2017
• Sequence Number: 18
• Publication Date: September 18, 1952
• Content Type: REPORT

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e Cata~ is Ox~.dation of Amonia ;
Invest3. at~.on of th
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1, Uri~ko, and N. P, Galenko
by M, V, Po~.yakov, V.
XV No ~.2, pP X60-1~6$,
Zhur F~.z Khi~a, Vol. ~ ,
Rus~~.an Mo per, ~.957~
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~ o Uac~.zka ~ and,
N. Ga~snkQ
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a.n tha ca.ta~.ytl.c
er of ~.aboratoxy studie?~
xn a numb
to nitro 'en ax~.dc~, tho ~xi;~tence of opta.mum 1
oxidation of ammonia ~
a ~ durations was es'~s,b~,ished botween the
temperatures and cont c
nv~tia mix'l,ure anr.1 the cata~.yst a p~.atinum screen,
aa.r~-amr
rotates be~.ow the optimum and excessa.ve~.Y' ~,arge ;
tempe
t!;aus stream th� ~rie~.d of nitrogen ax~.de de~ `
ve~.aca.ta.e5 of l,l';e gas ~
I
, of assa e off' unreacted ammonia, w]~i~.e at tempera
cxeases because p ~
mum and excess ve~.y' ~.ovr ve~.acities of 'the
tunas above the ap i
onsa.derab~.e part of the ammonia is convex�~,ed
gaseous s~l;ream, a c
not into nitrogen oxide but into nitrogen,
tudies a ~.inear corre~.atian b�tween temperature I
xn several. s
? Lion was estab~.ished wh~.ch is optimum insaf ar as ,
and contact data
' 'e~.d is concerned. ~mp~.r~.caJ. formu~.as have been 5
t nxtragen oxa.de ya~
,d to ex teas this corre~.ation (1,., �
propose p
I
of in~resti atians the anoma~.ous effect. of ad~ ,
In a. number g
. , of nitro en oxide was detQCted. Far examp~.e,
ma.x~ures an t~.e ya.el.d g
t4:
I
' to es of h drogen su~.f. ide introdl~ced under. cond.-~
vexy sma~.~. admxs r Y .
v
than a timum for nitrogen oxide production, increase
;
Lions other p ~ ~ '
t YP
i...
after b ~ to 6 percent (6) and even by 20 to 30
the yie~.d of the Y
;
~r
I;
arse 'dime there is observed a shift opta.~-
I.~ percent (7). At the s
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 Declassified in Part -Sanitized Copy Approved for Release 2012/04/26 :CIA-RDP82-000398000200120018-8
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morn oandit~on towards the ~.awc~x~ t~amper~a~turt~s (fxem $aq to ~'q0
degrees Ce~~ti~rada),
i' ~n sevara~. stud~.es (x,97 ~,n~taxm@d~ata products have bean '
~,so~,a~tad, for axamp~.e, ~.m~,d, hydroxy~am~.ne, nitrous and n~.trir,
ac~.d,
~'he 'thus derived naturrt~, ~,aw~~ and facts as wc~~~. as their
ana~.agu.es have becama th� faundat~,an of va.xa.aus hypa~th@ssw concer~
ning the mechan:~sm of c~cta~.yt~.c oxa.datic~~a of ammonia, I~er@ we may
ment~,on on~.y tha concepts of a hetprag@neous-~hamog@neQlrs reaC~t~.an
mechan:~sm, inasmuch as ~th@se concepts are mast c~.ose~.y assoc~.atnd
w~.th the cued natural ~.aws and facts
Accord~.ng to ono concept (~.0'~.~.), there occurs on ~~he sux-~
face of th� cata~.yst a decompos3.t~.an of ammonia to tlas imid and ox3.~
dation of the thus ~.iberat@d hydz~agen 'to water. Under candidions
which are not optimum far the praduct~.an of nigragen ox:i.de at ex-
cessa.ve~.y-high temperature ~.eve~.s and contact Mmes, a hetero e~
a
neau.s canversa.an of imid into
na. ro en tales
.ace and, and. tie
g
p ~
n
' evaporation of imid at the proper time ~.nto the react~.an space can
tributes (under apt~.mum conditions} to its homogeneous canverszpn
to I1ydro~^~.amine according to the equat~,an NH * H~0 NH~OH, and
y
thereafter th~^ough a number of ~.nteaMmediate stages into nitrogen
oxide,
r~~
V
r ~ 'ti1
~
According to cohcept of Markav , the atomic oxygen
;:r;,
a~~'
farmed upan~ why surface of the cata~.yst yie~.ds with ammonia, under
7
4,~ ~
0 ta.mu111 On
t 0
c da.
r~ f
s asst h dro amine th
a d e
n n
na t
p ra e
Y ~ g n oxa.de .and ~

a~ 9~~ 1~~te1"':
.ned by
assumed that this increase in 'the yield a~' nitxogc:n
su1.:~ide ~ We
t
' the requ~.t off' a decreased deM~'ixation a~' ammonia on the '~E
axldD zx
f ue to the oisoning o~ these walls by ,I`~~
walls of the quartz vexs el d p
~,j,
~ ,
the action a~ hydrogen sua.fide,
a
However before the exp~rirnentx referred to were staxted,
, ~,,aG,.
and that removal of the screen from the react~.on vessel ~~t
it was v~p~
f o
k v;
. t~
to removal of the p~.atinum; the. latter 3.n
does not ensuxe comple
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n ~k~e ~'oxrtl o~ ~ dus'~ covers ~ con~~.darab~e ~aaxb~.on q~ ~~he wa;~~.s,
anbr:~b~ab~.n, thereby ~bou~ ~a ba ~Q p�rcgn~ a~ the caba~.yab acM
c ~
' b~ ; the ~.6~d 0~ T~~,brOgen OX~.dQ decrsasQ~, ~a~,~,gw~.ng removal. .
~xv~ f ~
off' 'bhe screen ~xom 9~ ~0 9~ percvnb ~o ~~Q ~o ~Q percenb� r
Th~,s ~acb revaa~,s bhe acbivat~on meahan~.sm off' a p~,a~~.num
t over a eriod off' many hours, which ~.s atba~.ned by passa.ng
caba~.ys p
throe ~r bhe vessel. bhe r�act ion m~.x'~ure ab bemperabures oaf 'bhe
g'
arder o~''~00 to $00 degrees Centigrade,
The mechanism o:~ caba~.yst activation is c~.ear~.y nob ~,imi-
bed to than e o~ struc'~ure ar suri'ace area a~' 'bhe p~.abinum scxeen�
g
burin bhe activat~.oza process a poxbian o:~ 'bhe vessel. wa~.:Ls be~-
g
tames tasted with platinum dust, wt~ic~i necessari~.y causes a can--
siderable increase off' cabaly~t suri'ace and, what is nob less im~
ortant a decrease oi' 'bhe wall suz1face taking pare in defixabian
p ~
of ammonia and decreasi~~g th� yield a~' nitrogen o~ide�
,~f
Cui^ve l~C in Figure $ illustrates whab bakes plc.ce on eorn~
fete removal o:~ ~~he platinum by repeated treatment o~ bhe vessel
p
;
wibh a ua regia and boa.ling disti1.led water� This curve shawl de--
cam ositian of ammonia as a ~'uncb~-an off' ~~emperature ~.n a vessel. M
p
~`r
' m liter er minute},
a l
to
free a~ plat~.nuta ~veloc~.ty a~ gaseous s r p
~.y
' am ostian l0 bo 20 percent} is .appreciable even at ~ .
. Th~.s dec p ~ a
tom era.'tures below 5n0 degrees Centigrade,. and ~~eaches al'+nost lC0 ...~~....f
p
~
~rcent at tem erat~~res off' bhe order of 1000 degrees Centigrade,
p p ~,I~
~,d
}I
Cu~~'e T o~ Fi re $ shows bhe .dependence of nitrogen oxide k~~'
t~r, ~
~r~
~ nn the bem erat'ure, under identicalcondibians and witha.n
y~.elds p
y ~
r~;
2~
a r~~
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Rio p~~d~t~en o~ ammvn~.a b means a
the soma uses�~, aata~,~ Y Y
p~,at~.num screon, A apmpaxisan Q~ 'th~a ~tw� cux~rgs ~sads ~o the conM
r~
g
c~.usian ~ha~; 'the x~.gh~; arm off' c~~rve ~.s the e~'~ec~ off' deM~ixat~.An
a
a~ amman:~a dawn 'to ni~rogan tc which cantribu'te~ tho sur~'ace off' ;
~i
~u.ar~tz tube wa~.~,s free from p~.a~~.nurn dust ~ Th~,s p~,r~~~,num ~.s pre ~v
cise~y the cause off' decrease ~.n de~~'ixat~,on b;y the vessel. wa~.~.s
a,n carnparisan with what takos p~.ace under nanWca~a~.~�t;~r, conditions
of the process (curve ~T~ ~ Tnsafar as 'the ~.e~''t arm a~ curve T
~.s concerned, it is connected primara.J.y with the passage off` unM
rer~c,'ted ammonia which increase, ova decrease o~ the temperature,
xt must be assumed that even under optimum cand:~tions we never
have a hundred percent a~idation o~ ammonia to nitrogen oxide be~
cause a sma1.1, portion a~' it ~.s converted to nitrogen, in which
process th� wa~.].s off' 'the vessel. take part, wh i'le another portion
passes 'through the scx^een wa.~hau�t rer~c'til1~;,
a
~ decornpasitian oi"
e,mmonia ,a
i;
Figure Comparison of Curve showing yie~.d off' nitrogen oxide as
a ~'un.c�tion off' 'the 'temperature (x} ;with the .curve sho~ying degree of ~ ; -.i
ammonia decomposition as a function a~ temperature (I~} . Space ve~-
~,ocitf of gaseous f~.ow ~,iter per. minuted Diameter of s~;reen 1.1~
w
0 ' at' o of NH ~ TI Decotn asi'tian o~ NH .
cenLa.meters. x~.d n. n , p 3 i
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Fxam ~'~.gure~ 9 snd ~p ~
um ~'o~;loYrs ~ fu~~y xe~u;~~x c�ux~se
tin
ammonia ~,n a vessel. fxae off' p~.m `
ndence cif amman~.a d�c~ampos~.`~~an, expressed r
~';~,g~ure 9 show; the depa
in thQ aas� of ve~,oc.lt~,es of the a~.r~ ;4
~,n pexcent, an the tempexatu,xe
~.iters er minute (curve , 2
ammon.~a m~~'ture ,~mQUt~ta.ng 'to 0 ~ ~ p
d ~.~.tars per m~.nu'te (cuz^ve T~:~} ,
tars per m~,nute (cux~'e , an ~
e endence of 'the peg^cen'~a~e of ammona,a
wha.~.e ~'~,guxe ~.0 shows the d p
mmonia s~;ream at 'temperaM
decampasit~on on ve~oczty of 'the aa.r a
Cent3.~ r
00 degrees ~'t
tunes of 600 degxees Cent. rade (curv'e x , 7
00 de. reel Cen'tigx~ade (curve ~x~) ,
grade (curve I.~) , and $ ~

i
~ decomposi~,ion of '
ammonia
non:~a decompas~.t~.an with participation of
Figure 9. Degxee of a~u
a function of temperature, a't space ve1.a~
uart~ vessel. wal~.s, as
airy-ammonia mixture amounting to 0 � ~
c~.'ty off' gaseous stream o.~
. 0 7.i'ters ex rninu'ta (curve xT), and
1i'ters per m~.nute (curve , 2 ~ p
acre cen~-
r minute (curve ~:C:C) ~ Surface of wa~.1,s 52 a~
1~,0 ~.a.ters pe
2I 0 ~.iters per minute;
timeters ~ 0 e 5 ~,ibers per m~.nute, s
inu~te,
S:C:C 1~,0 ~.iters per m. i'
Y
~~`r
2l~
~ t
y
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' Declassified in itized COPY Appro
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'i

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4
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t~~..
t
~�r,
~ decampos~.t~.on o~
r
~mmona.a
g'. ;y
Ve~.aca.ty o;~ has ~'~,aw ~,n 1/m~.n
' e 0, Ue xee a~' amman9.a decampastia~l w;Lth participat~.an a~'
Fa.~ur
uartz vessel. wa~.~.s as a functa.an o~ space ve~.aci'~y a~ gaseous
q
eam of ~ix~.ammana.a mixture at a ~~campexature a:~ 600 de~raes Oen~
str
rade r curve I) 700 degrees Centigrade (curve and $00 de~-
` 9
i
tees Centigrade (curv'e ~T:C) , Sur~'ace o:~ wa~,~.s square cen~
g
5, ~ ercen~~ o;~ NH decomposition at 600 dogrees; x:C,
ta.meter , p 3
~ o~ decam ositian at 700 degrees; x:[:C, percent of NI~~ de~-
percen p
compasitian at $00 degrees,
r' menu nn decomposit].on of
fe~ea. .
0
et~.ta.on
Sat.Lsfactory r p p
onia is a anent :from a comparison of curve fix, Figure and
amm pp
~ x Fi. re 9, these curves were obtained at different times
c ~rve , ~
by differ�nt warkers~
b
~I.. ul~.
~
_ ,`~1~
i~~ ~ decompos it~.on ai' Y,,~f
{'4j
I,;r
,,i
ammona.a '
. sy
Fi re De tee of ammona.a decornpositian with part,icipatian of
~ ~
of tem erature at space ve~.ocity
quartz vessel. ~a~.~:s as a funct~.on p
k`~
u stream of nitrogen ammonia mixture amounting to 0.~
of gaseo s
~ C~
er minute (curve S) , and 2 ~.iters per minute (cux~re x~)
~.~.ters p
2~
~ ~
F
~
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(~'~,~uxa c4at ~ d)
u acs p~' wa~~,s square ec~n~~~metQrs ~ ~a Q ~ ~ ~,~~ars psr m~~ ~ ,
~ ~
Hato; ~ ~~.tars per m~,nu~p
t
j r,
shows 'rho pax^cen~ago a~' ammon~.a dacompas~,~~.an as
a ~u,nctian o:~ `ohs tempexa'tur~a ~'or two ve~.oc~.t~.es o~ th� gaseous
f n~.tra enMammonia mix'~ure ~ ~ percent off' ammon:la) , Cure
s~,xaam a ~
T re~.ates to spaca vel.oc~.ty v~ 0, ~ ~~tt~rs per m:tnute wh~.~.e aurae
x:C re~.a'~es to ' thQ ve~.oait:T of 2 ~.~.te.rs par m .nute,
Com orison a~ data shown in Figures ~;l and 9 ~.eads ~a a
p
cona~.usion concerna.ng the parta.c~.patian off' oxygen o~ ~~he ammonia
a~.r m~.x~~~ure in tk~e exotherml.a oxidation o~ ammonia to nitrogen; ;
a.t increases the rate off' ammonia clecomposita.on several, Mmes by r; a
aom orison with that obtained air decomposition of ammonia in the
p
' presence of
n~.~trogen, i

r
decomposition of.

r
ammona.a `
'u
;til
t
: ~r.
~,i.
~ ~ ee off' ammonia decomposition with participation of ~
~';~gure ]~e~,x
a~~~
uart~ vessel. wal~.s as a function o~ temperature without admixture
~~r
ri
off' h dro en su~.~'ide (curve x) , and with the air-ammonia mixture f
~ ~
0,1 eraent hydrogen su~.f ide. ~paae ve~.ocity o~ gas�ous
contan.ning p
Surface of wa~.~,s 52 square centimeters,
stream 2 ~.itars per minute.
x, without H25; ~:x, ~e~. percent HAS.
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