United States Patent 19 11 4,224,249

Kunz et al. (45) Sep. 23, 1980

54 TOLUENE DIAMINE FROM NON-WASHED Attorney, Agent, or Firm-Russell L. Brewer; E. Eugene

DNITROTOBLUENE Innis
57 ABSTRACT
75 Inventors: Nance D. Kunz, Bethlehem; Thomas This invention relates to an improvement in a process
A. Johnson, Orefield; Barton
Milligan, Coplay, all of Pa. for preparing toluene diamine. The improvement re
sides in a process which is capable of permitting reduc
73 Assignee: Air Products and Chemicals, Inc., tion of dinitrotoluene to toluene diamine without prior
Allentown, Pa. alkaline treatment for removal of nitrocresols in the
21 Appl. No.: 38,976
dinitrotoluene. In carrying out the improvement the
feed dinitrotoluene is water washed to remove HNO3 to
22 Filed: May 14, 1979 a level below 6000 ppm, and the catalytic conversion of
dinitrotoluene to toluene diamine is done continuously.
51. Int. Cl. ....................... C07C 85/11; CO7C 85/26 Dinitrotoluene is charged to a reaction vessel contain
52 U.S. C. .................................... 260/580; 260/582; ing a liquid carrier and reduced with hydrogen at con
260/689; 260/705 stant pressure, the dinitrotoluene being added at a rate
58) Field of Search ................................ 260/580, 582 to maintain a concentration of dinitrotoluene of 0.0001
to 25% by weight of the total reactor contents while the
56) References Cited hydrogenation catalyst is maintained at a level from
U.S. PATENT DOCUMENTS about 0.1 to 3% based on the weight of reactor con
tents.
3,546,296 12/1970 Gobron et al. ...................... 260/580
Primary Examiner-John Doll 5 Claims, No Drawings
 4,224,249 2
1.
lytic hydrogenation of dinitrotoluene. The improve
TOLUENE DAMNE FROM NON-WASHED ment resides in the ability to utilize a crude dinitrotol
DNITROTOLUENE uene feedstock prepared by the mixed H2SO4/HNO3
acid nitration of toluene which has not been subjected
BACKGROUND OF THE INVENTION to alkaline treatment as a reactant. The improvement in
1. Field of the Invention the basic process of preparing toluene diamine by react
This invention relates to a process for producing withnon-alkaline
ing treated crude dinitrotoluene feedstock
toluene diamine from an impure dinitrotoluene reactant. lyst comprises: the presence of a hydrogenation cata
hydrogen in
2. Description of the Prior Art (a) water washing the crude feedstock to reduce the
U.S. Pat. No. 2,131,734 is typical of the early pro 10 acid concentration in the feedstock to less than 6,000
cesses for the liquid phase hydrogenation of dinitrotol
uene to toluene diamine. Typically, the hydrogenation ppm, if above;
(b) continuously introducing dinitrotoluene and hy
was carried out in the presence of nickel supported on a
silica substrate and in the presence of a small amount of drogen to a reactor vessel,
an alkaline substance such as caustic soda. Typical 15 (c) maintaining a concentration of dinitrotoluene
amounts of catalysts were 0.5-2% catalyst metal by from about 0.0001 to 25% by weight;
weight of the dinitrotoluene. Temperatures were from (d) maintaining a hydrogenation catalyst concentra
80 to 140 C. and pressures were from 200 to 500 tion of about 0.1 to 20% by weight of liquid reaction
pounds per square inch. mass; and
U.S. Pat. No. 2,976,320 represented an improvement (e) utilizing a hydrogenation catalyst containing a
over the early liquid phase hydrogenation processes of metal selected from the group consisting of nickel, co
dinitrotoluene. In that process, the temperature of reac balt, chromium and iron.
tion was reduced to less than 100° C. to prevent hazards Several advantages are associated with the improve
due to the instability of the dinitrotoluene. Low temper 25 ment of this invention, and these advantages include:
ature hydrogenation was accomplished by first reduc an ability to hydrogenate dinitrotoluene without
ing the nitrocresol content in the feed and then using a prior alkaline treatment for reducing alleged catalyst
palladium or platinum catalyst to effect hydrogenation. poisoning nitrocresols and nitrophenols;
It was reported that nitrophenols or nitrocresols, which an ability to eliminate alkaline treatment of dinitroto
are normally present in commercial dinitrotoluenes, are 30 uene without adversely effecting hydrogenation condi
catalyst poisons and decomposition accelerators, and tions, thus saving on the expense of chemicals;
that by limiting the concentration to less than 500 ppm, an ability to reduce the problems associated with
and preferably 200 ppm, a dinitrotoluene could be hy environmental disposal of nitrocresol and nitrophenol
drogenated safely at low temperatures. One of the typi salts as associated with the prior art by virtue of the
cal ways of removing the nitrocresols and nitrophenols
was by washing the crude dinitro product, obtained by 35 elimination
an ability
of the alkaline treatment; and
to hydrogenate non-alkaline washed dini
separation from the spent nitration acid, with dilute trotoluene without noticeable loss of catalyst life or
aqueous alkali (e.g., sodium carbonate solution). The product, toluene diamine purity.
product then was water washed.
U.S. Pat. No. 3,093,685 discloses a liquid phase pro DESCRIPTION OF THE PREFERRED
cess for reducing dinitrotoluene to toluene diamine with EMBOOMENTS
the improvement residing in carrying out the reduction Dinitrotoluene which is used as a reactant in the
in the presence of water of reaction with no other sol present process is produced conventionally by nitrating
vent or diluent being added.
U.S. Pat. No. 3,356,728 differs from the patents previ toluene using the mixed acid technique. In this process,
ously cited in that it relates to a continuous process for sulfuric acid,isand
45 the toluene reacted with a mixture of nitric acid,
water under conditions effective for
reducing dinitrotoluene to toluene diamine. It was dis producing dinitrotoluene. Conventionally, the crude
closed that various operating problems such as poor
catalyst life and operating hazards due to the instability adinitrotoluene is removed from the reactor, passed into
phase separator and the product. separated from the
of the dinitrotoluene could be minimized by using the 50 aqueous
continuous process wherein the catalyst was present in product isacid phase. Further purification of the crude.
effected by washing with water to remove
about 2 to 25% by weight of the slurry with extremely
low concentrations of dinitrotoluene as the reactant. contaminant acid material followed by treatment with
The level of nitro compound was maintained at 0.15 an alkali, e.g. sodium carbonate to reduce the level of
pound equivalents nitro groups per pound of catalyst. nitrocresols and nitrophenols (nitrophenolic material) in
Temperatures of 100-140 C. and pressures of 55 the dinitrotoluene product. As noted in the prior art, the
100-2000 psig, preferably 200-500 psig hydrogen were primary purpose of the alkaline treatment was to re
move the nitrocresols and nitrophenols as these compo
used. Raney nickel catalyst was used in the hydrogena nents were believed to reduce catalyst life during the
tion procedure. reduction of the dinitrotoluene to toluene diamine.
U.S. Pat. No. 3,546,296 relates to another continuous
process for producing toluene diamine by the reduction 60 The process of this invention can tolerate crude dini
of dinitrotoluene utilizing specific reactor equipment. trotoluene which has not been treated with alkaline
Again, the concentration of dinitrotoluene in terms of material as a reactant and even permit concentrations of
the catalyst is extremely low so as to reduce operating nitrocresols and nitrophenols to at least a level of 1200
hazard. parts per million (ppm). Under the batch processes,
65 these concentrations of nitrocresols and nitrophenols
SUMMARY OF THE INVENTION could not be tolerated as evidenced by U.S. Pat. No.
This invention relates to an improvement in a contin 2,976,320. Although not intending to be bound by the
uous process for preparing toluene diamine by the cata ory, it is speculated that the batch hydrogenation pro
 4,224,249
3 4.
cess was not sensitive to nitrocresols and nitrophenols The following examples are provided to illustrate the
as reported but rather was sensitive to acid. This belief invention and all the parts and percentages are by
is based on information from the continuous process of weight unless otherwise specified.
this invention which shows an acid concentration of
above 6,000 ppm seriously diminishes catalyst life and 5 EXAMPLE 1.
increases tar while the reaction appears relatively insen The hydrogenation of dinitrotoluene was conducted
sitive to nitrophenolic material. In the prior art the in several runs to determine the effectiveness of the
alkaline treatment not only removed both nitrocresols process. The reactor used was a stirred one liter Parr
and nitrophenols but also the acid, and apparently based 316 stainless steel autoclave. The dinitrotoluene was
on the improved results obtained it was perhaps 10 charged to the autoclave on a semi-continuous (pulse)
wrongly concluded that catalyst life was sensitive to basis with the product being removed from the auto
nitrocresols, etc. rather than acid. Based on experimen clave in corresponding intermittent relationships so that
tal data water washing of the contaminated dinitrotol a constant volume of 500 milliliters was maintained in
uene is all that is necessary in the continuous process if the autoclave. The crude dinitrotoluene fed to the reac
the acid concentration is above 6,000 ppm. Water wash- 15 tor had the following general analysis and was obtained
ing is usually conducted so the acid level is 2,500 ppm from a commercial production unit after it had been
or below. washed with water (WW DNT) but not being exposed
The temperatures and pressures utilized in the pro to sodium carbonate treatment. The control was both
cess remain unchanged from the prior art and, for exam water washed and carbonate treated.
ple, such temperatures are generally from about 50 to 20
200 C. but preferably at a temperature of from about Dinitrotoluene 99.0%
90° to 130 C. Hydrogen pressures of 25-2000 psig can Nitrophenolic material 0.080%
be utilized, but generally the pressures are from about Nitric Acid 1200 ppm
100-250 psig. Balance approximately 1%
The hydrogenation of dinitrotoluene is carried out in 25
the presence of a hydrogenation catalyst. Any of the First the autoclave was charged with 500 ml of a
various non-precious metal catalysts which have been mixture of 60% toluene diamine and 40% water by
disclosed in the prior art promoting this reaction may be weight containing about 0.4% by weight pyrophoric
employed. These catalysts may be pelleted, granular, or Raney nickel catalyst having a particle size of from 1 to
powdered, although the powdered form having a parti 30 350 microns. Then the contents were heated in the
cle size of from 1-350 microns is preferred. Metals that
can be used for forming the catalyst are nickel, nickel autoclave to a temperature of 130° C. and then the
autoclave was pressurized with hydrogen. Although
promoted by cobalt, chromium, molybdenum and iron. the operation was a semi-batch mode because of inter
Raney nickel type catalysts are the preferred catalysts mittent feed and intermittent removal of product the
since in the continuous process they are relatively insen 35 operation was deemed continuous because the auto
sitive to nitrophenolic material. The hydrogenation clave remained at substantially constant volume and the
catalyst metals may be present on a support such as pulse rate was relatively rapid. The dinitrotoluene was
kieselguhr, silica, silica-alumina, and alumina although fed to the reactor at a rate of 1.45 gms/minute which
in the preferred case the Raney nickel type catalysts are translates to turnover numbers of 43.6 parts DNT re
unsupported.
The proportion of hydrogenation catalyst utilized in duced per hour per part catalyst and a maximum con
the reaction is quite low, e.g. from about 0.10 to 20% centration of about 0.3% DNT. The average reaction
time allowed for the dinitrotoluene was about 1-1.5
preferably from about 0.1 to 3%. When the concentra minutes even though the reduction takes place almost
tion of catalyst exceeds about 2% by weight little im instantly.
provement is realized. When the catalyst level falls 45
Table 1 represents two runs, one as a control wherein
below about 0.1% by weight there is insufficient cata the dinitrotoluene had been exposed to sodium carbon
lyst to effect rapid hydrogenation of the dinitrotoluene ate treatment with the result that practically no nitro
and long residence times are required. phenolic material or acid was present (control) and the
The proportion of dinitrotoluene is maintained in a other using
proportion of 0.0001 to 25% by weight of the reaction 50 material hadthe feed above wherein the nitrophenolic
mixture. Preferred results utilize a concentration of acid due to waterbeen
not removed but only the residual
washing (WWDNT). Results are as
0.01-3%.
follows in Table 1. Catalyst concentration, pressures
and other variables are given.
TABLE 1.
Run #1 Run #2
Control WWDNT
Temperature (C.) 130 130
Pressure (psig) 160 160
Catalyst Conc. (wt.%) 4(a) 4(a)
Operating mode incremental feed() incremental feed
Vapor phase H2 Concentration (%) 100 100
Catalyst Feed Mode batch batch
- - gmol H2 1.37 x 10-4 9.34 X 10-5
Initial Activity
(min) (gm cat) (cm)
Tar generation (%) 0.2-1.3% 0.1-2%
Turnover part DNT 43.62 43.62
hr. part cat.
Catalyst life-partPNT- 1975 1885 (minimum)(c)
part cat
 4,224,249 6
TABLE 1-continued
Run #1 Run #2
Control WWDNT
Deactivation rate initial rate
-0086%. gn initial rate
DNT reduced
-009.1% gm DNT reduced
97,
Material balance closure (%) 94.7
(2 gms of catalyst in 500 gm reaction mass
With pulse-in, pulse out systems autoclave liquid volume was maintained at 500 ml.
Experiment terminated at this point; exhausted dinitrotoluene feed stock.
The results show that water washed dinitrotoluene
could be hydrogenated without an adverse effect on
catalyst life or rate of reaction. The catalyst perfor -continued
mance in Run 2 was substantially the same as Run 1 and FEED Compositions
it was lower only because of an exhausted feedstock. 15 Run #3 Run #4
Tar generation was slightly higher in Run 2. This value Control WWDNT
Feed
may not represent any greater loss of material since tar Analysis/Sample DNT Feed
generation in Run 1 does not include the nitrophenolic Oxalate (ppm) 0.2
2.47 0.4
170 44
material removed by alkali treatment. Acetate (ppm)
20
. . . . EXAMPLE 2. The results are given in Table 2. . . .
The procedure of Example 1 was repeated except The results in terms of catalyst activity and reaction
that different feed and higher catalyst concentrations rate for both the control and the water washed dini
were used. The feed analyzed as follows for the alkaline trotoluene appeared to be similar. Slightly higher tar
treated dinitrotoluene feed and the water washed dini 25 generation with the water washed dinitrotoluene, was
trotoluene feed. noted. It is also noted the reaction is relatively insensi
TABLE 2. tive to nitrophenolic material as the concentration was
about 700 ppm. Table 3 below represents analysis of the
Run i3 Run i4
Control WWDNT percentage tar versus the grams of dinitrotoluene re
Temperature ("C.) 130 130 duced per gram of catalyst.
Pressure (psig) 160 60 TABLE 3
Catalyst Conc, (wt.%) 1.7(a) 1.7(a)
Operating mode incremental feed() incremental Tar Analyses (wt %)
feed(b) Run #3 Run #4
Vapor phase 35 Gms. DNT % Reaction Control WWDNT
H2 Concentration (%) 100 100 Reduced Per Mass Produced DNT DNT
Catalyst Feed Mode batch batch Gm. Catalyst From Feed % Tar (ppm) % Tar (ppm)
Initial Activity 3.67 x 10-5 3.67 x 10-5 0. 0. 0.42 5.0 0.482 5.0
gmol H2 59.5 5.9 1.02 5.0 0.888 5.0
(min) (gm cat) (cm) 6,8 76.4 1.28 50 0.99 5.0
Tar generation (%)() .4-1.28% 48-1.75% 40 175.3 88.6 1108 5.0 1.30 5.0
Turnover part DNT 2.03 21.03 233.2 94.4 1.27 5.0 1.54 5.0
hr, part cat. 289.1 97.24 0.904 5.0 1.66 5.0
Material balance 95.5 96.8 300.2 97.7 1,28 5.0 1.75 5.0
closure (%)
(a8.5 grams catalyst in 500gm. reaction mass
(with pulse-in, pulse-out systems autoclave liquid volume was maintained at 500 45 Table 3 shows that the tar concentration is slightly
ml. higher for the water washed dinitrotoluene feedstock
particularly at higher levels of dinitrotoluene reduced
per gram of catalyst. Even so the percent tar produced
FEED Compositions is relatively insignificant in terms of the benefit gained,
Run if3 Run #4 50 i.e. the ability to eliminate the alkaline treatment of
Control WWDNT dinitrotoluene and associated high chemical cost. Also,
Analysis/Sample DNT Feed Feed the process eliminates the environmental problems asso
Water (ppm) 4400 4800 100 ciated with the alkaline treatment.
Freezing pt. ("C.) 56.2.1 57.1 0.1
Acidity (ppm as H2SO4) 3000 - 200 55
EXAMPLE 3
Alkalinity (ppm as KOH) Nil Ni The procedure of Example 1 was repeated in order to
Cresols (ppm) 8 1 700 - 0
2,4,6 TNT (ppm) 730 - 40 100 + 30 determine the sensitivity of the process to acid concen
nitrobenzene (wt.%) 0.01 0.02 tration. The DNT feedstock used was product DNT
o-nitrotoluene (wt.%) 0.02 0.01 (control) spiked with nitric acid to an acid concentra
m-nitrotoluene (wt.%) 0.01 '0.01
p-nitrotoluene (wt.%) 0.02 0.01 60 tion of 10,000 ppm. The 10,000 ppm level was used as it
2,6 Dinitrotoluene (wt.%) 19.4 17.73 approximates the acid concentration of crude DNT
2,5 Dinitrotoluene (wt.%) 0.75 0.68 prior to water washing. In carrying out the test the
2,4 Dinitrotoluene (wt.%) 75.44 77.17 spiked DNT was continuously added to a reactor con
3,5 Dinitrotoluene (wt.%) 0.03 0.03
2,3 Dinitrotoluene (wt.%) 1,62 1.47 taining 40% H2O and 60% toluene diamine. During the
3,4 Dinitrotoluene (wt.%) 2.46 2.23 65 addition the acid concentration was monitored. The
Normalized isomer ratio 2,472,6
Nitrate (ppm)
79.7/20.2
0.3
81.3/18.7
092 - 20
hydrogenation was compared with water washed
Nitrite (ppm) 0.3507 60 - 8 DNT.
Sulfate (ppm) 0.69 0.26 230 - 50 The results are in Table 4.
 7
4,224,249
8
TABLE 4 stock without alkaline treatment with hydrogen which
Product DNT with
comprises:
WW DNT 10,000 ppm HNO3 (a) water washing the crude feedstock to reduce the
Initial Acitivity acid concentration in the feedstock to less than
(mol H2/min. g cat. cm) 3.67 x 105 6.0 x 10-5 5 6000 ppm;
Final Activity
(mol H2/min. g cat. cm) 3.67 x 10- 2.03 x 10-5
(b) continuously introducing dinitrotoluene and hy
Tar Generation (Wt. 7%) 1.7 4 at 6000 ppm drogen to a reaction vessel;
HNO3 (c) maintaining the concentration of dinitrotoluene in
10-30 above 6000
O
a range from about 0.0001 to 25% by weight;
Catalyst Life
ppm HNO3 (d) maintaining a hydrogenation catalyst concentra
gm DNT/gm cat. 800 220 tion of from about 0.1 to 20% based on the weight
Nitrobody in reactor 5 5 below 6000 ppm of reactor contents; and
(ppm) HNO3 (e) utilizing a hydrogenation catalyst containing a
5500 above 6000 ppm
HNO3 15
metal selected from a group consisting of molybde
num, nickel, cobalt, chromium, iron and mixtures
thereof,
Final catalyst activity of the product DNT corrected 2. The process of claim 1 wherein said dinitrotoluene
for difference in volume to the activity of the WW concentration maintained in the reactor is from 0.01 to
DNT was 1.24x 10-5(mole H2/mingm cat cm). At 6000 ppm 20
3% by weight.
HNO3, based on feed concentration, the catalyst activ 3. The process of claim 2 wherein said catalyst level
ity had diminished by about , and shortly after the is maintained from 0.1 to 3%.
catalyst completely failed. 4. The process of claim 3 wherein said metal catalyst
What is claimed is: is Raney nickel.
1. In a process for preparing toluene diamine which 25 5. The process of claim 4 wherein the crude dini
comprises reacting dinitrotoluene with hydrogen in the trotoluene feedstock is water washed to the extent that
presence of a hydrogenation catalyst, the improvement the acid concentration issk notk above 2500 ppm.
for permitting reaction of the crude dinitrotoluene feed k s t

30

35

45

50

55

60

65