NOV. 17, 1953
A_ J_ SHMIDL
2,659,659
AMMONIUM SULFATE PRODUCTION
Filed D80. 7, 1950
24
EVAPORATOR
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AMMONIA
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SULFONATES
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AGIDSLUDGE
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SULFATE
1
INVENTOR.
Alber'f J. Shmidl,
BY
'
AG
NT.
Patented Nov. 17, 1953
2,659,659
UNITED STATES PATENT OFFICE
2,659,659
AMMONIUM SULFATE PRODUCTION
Albert J. Shmidl, Houston, Tex., assignor, by
mesne assignments, to Standard Oil Develop
ment ‘Company, Elizabeth, N. J., a. corporation
of Delaware
Application December 7, 1950, Serial No. 199,667
7 Claims.
(Cl. 23-119)
1
2
The present invention is directed to the pro
ence of strong sulfuric acid. Such sludges are
described in the patent to Wadley and‘ Horeczy,
duction of ammonium sulfate suitable for use as
a commercial fertilizer from sulfuric acid sludges
containing dissolved carbon compounds. More
particularly, the invention is directed to the pro
duction of substantially carbon-free ammonium
sulfate from sulfuric acid sludges containing
sulfonic acid bodies.
.
The invention may be described brie?y as in
volving ‘the admixing of sulfuric acid sludge con
2,425,584 of August 12, 1947. These sulfuric acid
sludges contain water in an amount in the range
of 1% or 2% and carbon compounds from about
5% to about 15%. The acidity of such acids
ranges from 85% to 90% H2304-
-
Also suitable in the practice of the present
invention are the sulfuric acid sludgesresulting
10 from the treatment of aromatic concentrates
taining dissolved carbon compounds, such as
with sulfuric acid to remove traces of ole?ns
'sulfonic acid bodies and alkyl sulfates, with an
hydrous liquid ammonia under conditions to
cause reaction‘ of the sludge and liquid ammonia
therefrom. For example, xylene and toluene
containing fractions may be treated with
to form a product including a slurry of am
to 18 pounds per barrel of aromatic concentrate
to form a sludge which may serve as a feed stock
monium sulfate crystals in a liquid ammonia
solution of ammonia soluble compounds. The
product is subjected to a separation operation,
such as ?ltration, centrifugation or decanting to ,
amounts of strong sulfuric acid ranging’from 10
in the present invention. Also suitable in the
practice of the present invention are the sulfuric
acid sludges resulting from the treatment of
recover the ammonium ‘sulfate substantially free 20 thermally and catalytically cracked naphtha
of carbon from the solution of ammonia soluble
with strong sulfuric acid.
carbon compounds in the ammonia.
The present invention will now be described
in more detail by reference to the drawing in
'
I
The separated ammonium sulfate crystals may
be subjected to a washing operation .with addi
which the single ?gure represents a preferred
tional quantities of liquid ammonia to remove
mode of the invention. Referring now to the
traces of ammonia soluble carbon compounds
drawing, numeral ll designates a charge line‘
while the solution of ammonia soluble carbon
through which a sulfuric acid sludge containing
compounds may be subjected to an evaporation
dissolved carbon compounds is introduced into
treatment to evaporate liquid ammonia there—
the system from a source not shown and is
from and to recover the ammonia soluble carbon 30 pumped by pump I2 into a reaction vessel I 3
compounds. These latter compounds are be
wherein there is maintained a body of anhydrous
lieved to be ammonium sulfonates which have
liquid ammonia at a temperature below 125?;F.
wetting and emulsifying properties.
Reactor I3 is provided with line I4 containing
The admixture of anhydrous liquid ammonia
a compressor I5 and a cooler I6. Vaporous am
is maintained under a suitable pressure to pro
monia is removed from the mixture of sulfuric
vide a liquid phase and the liquid ammonia is
acid sludge and anhydrous ammonia in vessel
allowed to evaporate to maintain a reaction tem
I3 to remove the heat of reaction and maintain
perature below 125° F. A suitable reaction tem
the reaction temperature below 125° F. The
perature may be in the range from 100° to 125° F.
Vaporous ammonia after compression to liquefy
The product including the slurry of ammonium
same is cooled in cooler I6 and is discharged by
sulfate in ammonia which is subjected to a sepa
ration treatment should contain at least 1 vol
ume of liquid ammonia based on the sludge.
The amount of liquid ammonia admixed with
the sulfuric acid sludge originally should be in
excess of one volume and preferably should be
in a ratio in the range of 3 volumes of ammonia
to 1 volume of sulfuric acid sludge. These
amounts will provide a su?icient amount of am
monia to carry the slurry from the reaction '
vessel.
»
‘The sulfuric acid sludge employed in the prac
tice of the present invention may suitably be the
spent sulfuric acid sludge derived from the
alkylation of isopara'?ins with ole?ns in the pres
line I4 into evaporator H.
>
The product containing a slurry of ammonium
sulfate crystals in liquid ammonia and a solu
tion of ammonia soluble carbon compounds in
liquid ammonia is discharged from reaction ves
sel I3 by line I8 into a separation zone I9- which
suitably may be a ?lter or a centrifuge. Alterna
tively, the separation zone I 9 may be a decanter.
For purposes of this description it is assumed
that separation zone I9 is a ?lter of the rotary
or leaf type. In separation zone I9 the am
monium sulfate crystals are removed from the
slurry in liquid ammonia and from the solution
of ammonia soluble carbon compounds and with
drawn from the system through line 20 as crys
2,659,659
4
3
a reaction temperature below 125° F. reacting said
talline ammonium sulfate substantially free of
sulfuric acid sludge and anhydrous liquid am
carbon. The cake formed in ?lter l9 may be
monia to form ammonium sulfate crystals, main
Washed with liquid ammonia, introduced in ?lter
taining unreacted liquid ammonia in the reac
I9 by line 2| from ammonia storage tank 22.
The ?ltrate containing ammonia and ammonia U! tion zone at all times and washing the ammonium
sulfate crystals formed in the reaction zone con
soluble carbon compounds is discharged from ?l
tinuously with. said unreacted anhydrous liquid
ter I9 byline :23: into line It iron; whence it is
routed into evaporator I];
ammonia, removing from said reaction zone as
In evaporator I‘! the temperature and/or pres
product a slurry of ammonium sulfate crystals
a liquid ammonia solution of ammonia soluble
sure is controlled to allow removal of ammonia 10v
therefrom by line 24 which on passage through
carbon compounds, said slurry containing at least
cooler 25 is lique?ed and then discharged by- line
one» volume-‘of unreacted ammonia for each vol
26 into ammonia tank 22.
ume of sulfuric acid sludge charged to the reac
It may be desirable under some conditions for
tionzone to forlmvthe ammonium sulfate crystals
the ammonia removed froinkgeactoi" vessel {31 by
line [4 to be discharged into ammonia storage
15
in, said slurry and separating ammonium sulfate
crystals substantially free of carbon from said
slurry.
tank 22 rather than into evaporator I]. When
this condition prevails, valve‘ 2'!‘ in line I4- is
2. A method in accordance with claim 1 in
closed and valve 28 in branch line 29
opened
which liquid ammonia is evaporated from the
allowing the lique?ed ammonia in line [4 to be 20 reaction zone to maintain the reaction tempera
discharged. into. tank 2.!- Anhrdmus liquid am
in. reaction vessel I3" ‘is suppliedfrom
tlilfe, Within-therange of 100‘? to.1v2,5°'F.
3-. A method in accordance- with claim 1 in
which the. ammonium sulfate crystals separated
from the slurry are washed with. liquidammonia
after the separation step.
4. A‘ method for producing ammonium sulfate
from sulfuric acid sludge containing dissolved
states tank 21 byline 3t'
Q. _ evaporatian of ammonia. from the solution
injevaporator I‘! the ammonia soluble) carbon
compounds arerecovered from evaporator I‘! by
line 3|.’ These compounds, are believed to com
Prise amm?nium. sulffonetes. and may ?nd use as
' '
carbon compounds and having’ a water content
within the range of 1% 120.2% which comprises
introducing said sulfuric acid sludge into abody
of anhydrous liquid ammonia maintained
a
and/0r. emulsifying. agents While the am
sulfate recovered by line 29 is substan
ti‘ally free of carbon and is of a substantially white
crystalline nature.
reaction zone at a temperature within the range
“As a further illustration of the present inven
tion, sulturiseszid Sludge. resulting from the. al
kylaltib'h of iéebutaee withtutyleeeswhich con
t'a
of 100° to 125° F., said sulfuric acid sludge and
anhydrous liquid ammonia being the only mate?
rials introduced into said. reaction zone, reacting
said sulfuric acid sludge andanhydrous liquid am-i
monia to forrnammonium sulfate crystals, main-v
- 4.13% by Weight Qf'Qis§91VQd carbon com.
pgunss ‘and 90%, by. weight or. 212E404 was treated
with 119111191 wine. 5 ' at? temperature below 125°
" 'it11._-f .
._-.,, .. its 9? the dissolved, carbon
ébmpege?'s. to termemoqupt incluqins 2». slurry
ofL ammonium sulfate crystals ammonia and a
solution of ammonia soluble compounds. Am
monium sulfate crystals were recovered and found
to contain only 0.12% by weight of ‘carbon. The
solution of ammonia soluble compounds was t
taining unreacted liquid ammonia in the reaction
Z9118. at. all times and washing, the ammonium
Sulfate crystals. formed. in. the. reactionzone. con
tinuously with said unreacted anhydrous liquid
ammonia, removing from said, reaction zone as
also an amber colored viscous liquid having a
productaslurry of ammonium sulfate crystals in
a. liquid ammonia, solution” of ammonia soluble
carbon, compounds, said slurry containing at least
one volume oi unreacted. ammonia for each vol-.
ume of sulfuric acidsludgecharged to the reac
characteristic acid odor.
tion
evaporated‘ to separate ammonia therefrom and
’
'
In another operation a sulfuric acid sludge, re¢
to form the ammoniumv sulfate Crystals
in s. d slurry, andssparatine. ammoniurnsulfate
Qry .als. silt-eta.I.1.t.ia1.1ivw free of. carbon from said
sulting from the treatment of a Xylene fraction -
with strong sulfuric acid, which had atotal car
bonfeontentof-Zlqb by weight was admixed with
anhydrous liquid ammonia at a temperature be?
slurry._
5.- A- .rnethqd. in accordance. with. claim. 4. in
low§1~25°v F. A product was‘ formed including a
reaqtignzons to maintainthe reaction tempera
which liquid‘ ammonia is evaporated from the
slurry: of-Isubstantially white ammonium sulfate
true. withiutherange of 1.00.?’ to 125° F.
'
6,4” method, in accordancev with claim 4. in
crystals ‘in at liquid ammonia solution of am
monia soluble carbon compounds. The am
monium sulfate was; recovered and found to‘ con;
tai'fi only 40.15%» by weight of-carbon and to pos
wblthths ammqnium. sulfate. crystals separated
flfql‘fl the. sllilil'y e136. washediwith liquid ammonia
after the separation step.
from, sulfuric acid sludge, containing dissolved
carbon compoundswhich comprises introducing
saidv sulfuric acid sludge into" aubody of anhydrous
pounds was subjected to evaporation and am
monium-sulfonates of a’ dark amber color. and of
a brittle nature were recovered.
These am
moni-um sulfonates are useful as wetting or emul
'
7-‘ smsthvd, f r. producing ammqniumsuliate
sass no odor.
'
The. solution. of" ammonia soluble carbon com
liquid; ammonia maintained in a reaction zone
65
at a temperature within the, rangerof loo to" 125,0
trated, ‘what I wish to claim as new and ‘useful
F; with thetulfuric acid. Sludge and- anhydrous
liquid. ammonia
the reaction 20218 being in
the proportion of’three volumes 0L anhydrous
liquid ammonia ps1". vqlume of, sludge, reacting
an'dto secure by Letters Patent is:
11A method for producing ammonium sulfate
said Sludge and liquid ammonia to form
ammonium sulfate crystals, maintaining unre
sif-yingagents.
'
'
They'nature and objects of the present inven
tion having been completely described and-illus
from sulfuric a‘cid'sludge containing dissolved
carbon compounds which’ comprises, introducing
seisi'stlfurit acid. sllldge. 111W? 199W 013 anhydrous
new ammonia meaning 11% rt'actiqazcne at
acted ammonia in the reaction zone at. all?times
75
and washing the ammonium sulfate crystals
formed in the, reaction zone continuously, with
said unreacted. anhydrous liuuid‘ammonia, evapo
5
2,659,659
6
rating liquid ammonia from said reaction zone
to maintain the reaction temperature below 125°
Number
1,346,106
1,360,785
2,022,813
F., removing from said reaction zone as product
a slurry of ammonium sulfate crystals in a liquid
ammonia solution of ammonia soluble com
2,025,401
pounds, said slurry containing at least one volume
2,026,250
of unreacted ammonia for each volume of sul
furic acid sludge charged to the reaction zone to
Number
form the ammonium sulfate crystals in said slurry
and separating ammonium sulfate crystals sub 10
152,766
stantially free of carbon from said slurry.
365,945
109,269
ALBERT J. SI-IMIDL.
References Cited in the ?le of this patent
UNITED STATES PATENTS
Number
Name
Date
1,310,306
Sperr ____________ __ July 15, 1919
1,,
Name
.
'Date
Bredlek __________ __ July 13, 1920
Parrish __________ __ Not", 30, 1920
Ruys ____________ __ Dec. 3, 1935
Rutherford ______ __ Dec. 24, 1935
Pyzel et al ________ __ Dec. 31, 1935
FOREIGN PATENTS
Country
Date
Great Britain ____ __ Oct. 21, 1920
Great Britain ____ __ Jan. 28, 1932
Great Britain ____ __ Aug. 31, 1947
OTHER REFERENCES
Perry Chemical Engineers Handbook, Mc
" Graw-Hill, N. Y. 1940, pages 429, 2551.