FORM-2

The Patents Act

(39 of 1970)

The Patent Rules, 2003

-[See Section 10 and Rule 13]

COMPLETE SPECIFICATION

AN IMPROVED PROCESS FOR PRODUCTION OF HYDRAZINE HYDRATE

COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH

RAFI MARG, NEW DELHI — 110011, INDIA, AN INDIAN REGISTERED BODY -
Incorporated under the registration of Societies Act (XXI of 1860).

And

GUJARAT ALKALIES AND CHEMICALS LIMITED

P.O. PETROCHEMICALS-391346, DIST. VADODARA,
GUJARAT, INDIA
(Promoted by Govt. of Gujarat)

The following specification particularly describes the invention and manner in which it
is to be performed.
FIELD OF THE INVENTION
The present invention relates to an improved method for production of concentrated
aqueous solutions of hydrazine hydrate using recyclable solid activator for ketazine
formation and catalyst free ketazine hydrolysis.

BACK GROUND OF THE INVENTION

Hydrazine hydrate (N2H4.H 20), a colorless liquid having an ammonical odor, is the
simplest diamine and unique in its class because of the N-N bond. It was first
prepared in 1887 by Curtius from diazo acetic ester. In 1893 Thiele suggested that
the oxidation of ammonia with hypochlorite should yield hydrazine hydrate and in
1906 Raschig demonstrated this process, variations of which constitute the chief
commercial methods of manufacture in the 1990's. It is a mild base that is miscible
in polar solvents such as water, ammonia, amines and alcohols.

During the past fifty years hydrazine hydrate has emerged from an interesting
curiosity to a chemical manufactured in tons. Hydrazine hydrate has been known
since 1863, and in 1875 Emil Fischer prepared and characterized the aryl
compounds of hydrazine hydrate. It was in 1887 Curtius succeeded in isolating
hydrazine hydrate itself by the action of alkali on diazo acetic ester.

Raschig, following a suggestion by Thiele, showed that hydrazine hydrate could be

produced by the action of sodium hypochlorite on aqueous ammonia, the yield being
greater in presence of excess ammonia. Raschig found that 60-70% yields of
hydrazine hydrate could be obtained in the presence of glue or gelatin and attributed
this effect to the increased viscosity of the solution. Joyner showed that increasing
the ammonia:hypochlorite ratio increased the yield of hydrazine hydrate and the yield
was proportional to the amount of glue added when this was present in small
amounts. The manufacture of hydrazine hydrate by a similar procedure from urea
instead of ammonia was patented about this time, yields reported being 70%.

The discovery that hydrazine hydrate containing 15% methanol could be employed
as a rocket fuel when mixed with oxidizing agents such as nitric acid, hydrogen
peroxide or oxygen, stimulated the expansion of production of hydrazine hydrate in
Germany during the Second World War.
 3

The direct fixation of nitrogen and hydrogen to hydrazine is thermodynamically

unfavorable. Instead the commercially feasible process involves partial oxidation of
ammonia (or urea) using hypochlorite or hydrogen peroxide. Bayer first
commercialized such a process, using acetone and hypochlorite as oxidant. Another
process developed by Produits Chimiques Ugine Kuhlmann (PCUK) and practiced
by Atofina (France) and Mitsubishi Gas (Japan) involves the oxidation of ammonia
by hydrogen peroxide in presence of butanone and another co gnponent that
apparently functions as an oxygen-transfer agent. Oxidation of Benzophenone imine
also received much attention, but is not commercially used.

The first large scale use of hydrazine hydrate was as a fuel for powering the rocket,
a German ME-163 fighter plane during the World War II. Production in the United
States began in 1953 at the Lake Charles, Louisiana plant of the Olin Corporation
(now Arch Chemicals) a facility then having a capacity of 2040 metric tons. In 2004,
world capacity is approximately 462100 metric tons, reported as N 2H4 . Most of this is
in the form of hydrazine hydrate. Hydrazine hydrate and its simple methyl and
dimethyl derivatives have endothermic heats of formation and high heats of
combustion. Hence, these compounds are used as rocket fuels. Other derivatives
are used as gas generators and explosives. Hydrazine, a base slightly weaker than
ammonia forms a series of useful salts. As a strong reducing agent, Hydrazine
hydrate is used for corrosion control in boilers and hot water heating system; also for
metal plating, reduction of noble-metals catalysts, and hydrogenation of unsaturated
bonds in organic compounds.

Hydrazine hydrate is also an oxidizing agent under suitable conditions. Having two
active nucleophilic nitrogen and four replaceable hydrogen, hydrazine is the starting
material for many derivatives. Some among them are, as a foaming agent for
plastics application, in manufacture of antioxidants, polymers, polymer cross-linkers
and chain extenders, as well as in fungicides, herbicides, plant growth regulators and
pharmaceuticals. Hydrazine hydrate is also a good ligand; numerous complexes
have been studied. Many heterocyclics are based on hydrazine, where the rings
contain from one to four nitrogen atoms as well as other heteroatoms. The many
advantageous properties of hydrazine hydrate continued its commercial utility.
Hydrazine is produced commercially, primarily as an aqueous solution (which is
 4

known as hydrazine hydrate) typically in varying % by weight of hydrazine hydrate.

The following references serve as the prior-art for the preparation of hydrazine
hydrate by various approaches.

US4189411; US3972878; US3972876; US4093656; US3948902; US6562311;

US6482383; US6605265; US5986134; EP70155; CN100526237.

US4724133; US4725421; GB1164460; FR1315348; GB1174050; GB1211547;

US3607041; FR1506943. U s3 q 8)-1 PM?, t.) s cyj 04 3

Kirk Othmer, 3 rd edition, 12, 734-755; Journal of American Chemical Society, 1929,
51, 3394-3409; Ullmann's encyclopedia of industrial chemistry, 1989, A13, 182-183.

Though, several of these methods are practical at laboratory level, only some of
them are useful at industrial production. Most of these reported methods are difficult
to be practiced at the industrial production due to one or more of the following
factors: (a) stringent monitoring of the working solutions; (b) catalyst solutions with
varied ranges; (c) low reaction yield due to difficulties in impurity removal; (d)
operationally difficult reaction conditions/parameters; (e) catalytic hydrolysis of
ketazine to give hydrazine hydrate; (f) high energy requirements.

OBJECTIVE OF THE INVENTION

In view of the limitations in the prior art, the main objective of the present
invention is to provide an efficient process for the production of concentrated
aqueous solutions of hydrazine hydrate.
Another objective of the present invention is to provide a process for
production of hydrazine hydrate, using solid acetamide as the recoverable catalyst
for ketazine formation and catalyst free hydrolysis of ketazine to give aqueous
solutions of hydrazine hydrate.
Another objective of the present invention is to provide a process which
involves catalyst free hydrolysis of ketazine to give hydrazine hydrate with lower ratio
of water to ketazine (1:1.5), unlike the known methods, where a catalyst and higher
water ratio is required for hydrolysis.
Yet another objective of the present invention is to provide a method for
 hydrazine hydrate production, where all unreacted and excess substrates are
recoverable and reusable making it a highly energy efficient, clean and eco-friendly
process.

SUMMARY OF THE INVENTION

Aiming at the defects and limitations in the prior-art, we have developed a
new and highly effective, industrially simple and economically viable process for the
production of hydrazine hydrate. Briefly, the present invention features improved
process for production of concentrated aqueous solutions of hydrazine hydrates,
comprising:
reacting hydrogen peroxide, ammonia, and ketone to form an azine in presence
of an activator;
separating the resulting mixture from step (a) into a ketazine layer and a aqueous
solution layer;
concentration of ketazine and recovery of methyl ethyl ketone by evaporation;
purification of ketazine by vaccum distillation;
recovery of acetamide from aqueous layer by dehydration;
then returning the recovered methyl ethyl ketone and acetamide to step (a);
hydrolysis of the ketazine to obtain hydrazine hydrate and regenerating the
methyl ethyl ketone;
and recycling the methyl ethyl ketone to the stage (a),
(i) concentration of hydrazine hydrate obtained in stage (g) to obtain 40-80% of
hydrazine hydrate.
The present process can be performed easily and is a very economic strategy which
is most viable for industrial scale.

DETAILED DESCRIPTION OF THE. INVENTION

The present process for the production of concentrated aqueous solutions of

hydrazine hydrate is described as follows. This process is the most convenient and
simple approach based on methyl ethyl ketazine route involving the following stages:
 6

General Process description

In this process, hydrogen peroxide, gaseous ammonia, and ketone are reacted to
form methyl ethyl ketazine which on further hydrolysis forms hydrazine hydrate:

H202 + 2NH3 + 2(C2H5)(CH3)C0 (C2H5)(CH3)C-N-N-C(CH3)(C2H5) + 4H20

(C2H5)(CH3)C=N-N=c(cF13)(C2F15) + 3H20 N2H4.H20 + 2(C2H5)(CH3)CO

Methyl Ethyl Ketazine Preparation

Hydrogen peroxide in the form of 50 to 70% by weight is used to oxidize ammonia in

the presence of a ketone. Methyl ethyl ketone (MEK) or acetone is usually preferred.
The reaction of MEK in the presence of hydrogen peroxide and ammonia is carried
out at atmospheric pressure and temperatures ranging from 0 °C to 60°C. A molar
ratio of Hydrogen peroxide: MEK: Ammonia ( gas ) of 1:4:3 is taken as feed.
Hydrogen peroxide is activated by acetamide and ammonium acetate. The organic
phase of the reaction mass, MEK-Methyl Ethyl ketazine is fed to a pressure
hydrolysis column at a pressure between 2 and 20 bar (preferably from 8 to 12 bar)
and temperatures ranging from 150°C to 200°C (preferably from 175°C to 200°C).
The overall reaction for the methyl ethyl ketazine formation is:

H5C2 ,
, C2H5
H2 0 2 + 2 NH3 + 21-15C2:C=0 ,C=N-N =C, + 4H20
H3 C H3 C CH3

The mechanism of this reaction involves activation of ammonia and hydrogen

peroxide because these compounds do not react them self. It appears that
acetamide functions as an oxygen transfer agent, possibly as the iminoperacetic
acid, which then oxidizes the transient Schiff base formed between MEK and
ammonia to give the oxazirdine, with generation of acetamide.

One molecule of ammonia reacts with one molecule of MEK to form Schiff base.

NH3 + (C21-15)(CH3)C0 (C21-15)(CFI3)CNH (Schff base) + H2O

Hydrogen peroxide reacts with acetamide to form iminoper acetic acid.

 H202 H3C, H3C,
.C=0 ,C-00H + H2O
H2N
Hydrogen peroxide Acetamide Iminoper acetic acid

Iminoper acetic acid then oxidizes the Schiff base to give the oxaziridine and
regenerates acetamide.

1-15C2m= H3 C H5 C 2
NH + ,C-OOH H H3C, C=-0
H3C HN,c- H3C' H2N
Schiff base Iminoper acetic acid Oxaziridine Acetamide

The oxaziridine oxidizes a second molecule of ammonia to form a hydrozone

, 0
Hp-2"Nci\TH NH3 H5C2-... c =
N-N112 + H2O
H3C

Oxaziridine Ammonia Hydrzone

Hydrozone with excess ketone forms the methyl ethyl ketazine.

H5C2"--G=N-NH2 H5C2, H5C2,5

,C=0 C=N-N=C, + H2O
H3C 3
HC HC'
3 CH3

Hydrzone MEK Methyl ethyI ketazine

The last two reactions can be clubbed together as follows to give the methyl ethyl
ketazine

H C 0
- H C -- =
+ H5 C2c 0 = -C H
s 2 -C NH + N-1
; 1543 6 -C N -N C-01135 + H 2 0
H3 C HC
Oxaziridine MEK Methyl ethyl ketazine

The methyl ethyl ketone (2-butanone) forms an immiscible upper organic layer easily
removed by decantation. The lower, aqueous phase containing acetamide and
ammonia, is concentrated to remove water formed in the reaction and is then
 8

recycled to the reactor after a purge of water soluble impurities. Organic by products
are separated from the methyl ethyl ketazine layer by vacuum distillation.

Hydrolysis

The purified methyl ethyl ketazine is hydrolyzed under pressure (8.0-11.0 kg/cm 2 ) to
give hydrazine hydrate and methyl ethyl ketone overhead, which is recycled. The
hydrazine hydrate is concentrated in final vacuum distillation column.

FI5CT'C= N-N=C.C., TT
C 2H5 + 31120 H2O +
2 H5C2N.,c=0
H3 C u n3 H3C
H H

Methyl ethyl ketazine Hydrazine Hydrate MEK

PROCESS DESCRIPTION:

Preparation of hydrazine hydrate involves the following steps:

Methyl ethyl Ketazine preparation.

Concentration of methyl ethyl Ketazine / Recovery of MEK.

Purification of methyl ethyl ketazine.

Recovery and regeneration of acetamide.

Hydrazine hydrate preparation.

Concentration of hydrazine hydrate from 40 to 80%.

Methyl ethyl Ketazine preparation: A known quantity of Methyl ethyl ketone (MEK)
is taken into a reactor and acetamide is charged into the reactor along with
appropriate stabilizers. H202 is added in a controlled manner for 5 hrs at a rate of 10-
12 kg/hr, simultaneously ammonia is sparged into the reactor at a rate of 6-7 kg/hr.
The reaction is exothermic. The reactor is maintained at atmospheric pressure, at a
temperature of 50-60°C throughout the process by circulating chilled water. After
 9

addition of both the reactants (i.e., 6hr), reaction is continued for further 1 hr. the
reaction mass is left for settling. After 1 hour, organic and aqueous layers are
separated in a separator and stored in separate tanks.

Process Flow Diagram

Concentration of methyl ethyl Ketazine / Recovery of MEK: Initially, a known

quantity of organic layer is charged into an evaporator. Evaporation of MEK is done
under vacuum of 200 to 250 mm Hg at a temperature varying from 60-70°C. Then
the material is discharged into a reboiler for purification of methyl ethyl ketazine.

Purification of methyl ethyl ketazine: Initially, MEK fraction from the mixture is
collected under vacuum of 200-250 mmHg and temperature of around 80-90 °C.
Then gradually vacuum is increased to 20-25 mmHg with temperature in reboiler
around 80-90 °C. Collect initially intermediate fractions of ketazine and MEK mixture
into a tank, and then collect pure enriched methyl ethyl ketazine of 95% and above in
a separate tank.

Recovery of acetamide: Initially, a known quantity of aqueous layer is charged into

a reboiler which is maintained at 100-110 °C to remove 40-45% water. After distilling
out water, ammonia is sparged into the reboiler to convert the ammonium acetate
which is formed by hydrolysis of acetamide in base conditions during the formation of
methyl ethyl ketazine, into acetamide and to recover it, the temperature of the
 10

reboiler is increased to 140-145 °C and maintained for 9 hrs. Dehydration is carried

out till 65-70% acetamide is present in the bottom product. The product is cooled
and crystallized. The solution containing acetamide crystals is either centrifuged or
filtered under vacuum. Mother liquor separated from acetamide crystals is recycled
back to the dehydration column.

Hydrolysis Section

Hydrazine Hydrate is produced by hydrolysis of Methyl Ethyl Ketazine.

-C21-15
H5
5 2.:;C=N-N=C.„ + 3 H2O
H. H2O + n
3
HC un3 2 H3 C-
1-=‘-)

Methyl ethy 1 ketazine Hydrazine Hydrate MEK

General Operational procedure for Hydrolysis Section

As water is a reactant, the specification of DM water is to be maintained without any

deviation in pH (8.2-8.5) and conductivity (preferably >1.0 and always less than 2.0).

In a known quantity of DM water addition of 1-2ml of 80% hydrazine hydrate makes

the water alkaline with pH 8.2-8.5.

Perform pressure test of the hydrolysis column and the downstream equipment by
taking known quantity of DM water in reboiler and heating by circulation of hot oil, till
pressure of 10 bar is attained under total reflux. Note the temperature profile in the
column, pot, condenser and reflux drums (pot 180-182°C, column top is steam
temperature at 10barg, reflux 152 °C).

Ketazine is pumped at a rate of 11 1ph and DM water is pumped at a rate of 7 Iph

Operational parameters

The hydrolysis column is operated at a loading capacity of 60% (10.8-11Iph ketazine,

7.2-7.5Iph DMW)

1. Prepare required quantity of 20% HH solution in storage tank and pump to

reboiler.
 11

Circulate hot oil through the jacket of reboiler. Turn the hot oil heater ON and
gradually raise the temperature first to 100°C and then further. Pot temperature
to be maintained at 180°C and top column temperature between 174-175°C, by
setting the hot oil flow rate maintain the required temperature profile in the
column.
After getting the required temperature profile in the column, start feeding DM
water first, followed by ketazine after 5-10min.
Both the feeds are preheated to 100-120°C by passing steam in jacket of feed
lines, and mixing in a static line mixer before entering the column.
In the feed section of the column a spray type distributor is fixed to inlet line,
which sprays the water-methyl ethyl ketazine mixture on to a bed of ceramic
raschig rings packing of 6mm dia. The column has 2 nos. of 3 m each reaction
sections and 2 nos. of 2 m each MEK stripping section above feed section. The
column is provided with temperature indicators to measure the temperature
profile in the column. The re-boiler is a jacketed vessel where hot oil at known
temperature is circulated to heat the contents (20% HH taken at start of the run
and 40%HH as the reaction progresses) in the pot.
The hydrolysis column is operated under reflux (composition of reflux: water +
MEK).
The column pressure is maintained between 10.5-11bar. MEK released at
around 160-162 °C is collected at the top and recycled.

Passivation of Reactor with Hydrazine Hydrate: The hydrolysis column is washed

with DM water. A known quantity of 20 % Hydrazine Hydrate solution is prepared by
diluting fresh 80 % Hydrazine Hydrate (Purchased from market) with DM water and
charged into the reboiler. The reactor was flushed with N2 for 30 minutes. Hot oil
system was started and heating of reboiler was started. After the pressure in the
reactor attained 9 Kg / cm 2 the reactor was kept undisturbed for 12 hrs with constant
hot oil circulation for 12 hrs. During this period the reactor was under total reflux
condition.
 12

Hydrolysis experiment:

The DM water is feed at a rate of 6-7Iit /h with preheating it to 120°C. The column
was kept under total reflux condition by isolating the reflux drum. After 45 minutes
the Ketazine feed was started at the rate of 8.5 — 101it/h with pre heating to 120° C.
The pressure in the reactor reaches to 10.5-11 Kg/cm 2 . The column top temperature
falls reaches 160-161°C. At this stage take reflux drum in line and start collection of
top production. Maintaining the reboiler level, the bottom product is collected
continuously.

This process was continued till concentration of Hydrazine Hydrate reaches 40%. The
feed rates of ketazine and DM water were maintained at the molar ratio of 1:7.

Purification and Concentration of hydrazine hydrate from 40-80%:

The output from the hydrolysis column bottom was used for the concentration
experiment.

The unit is run initially with reflux ratio 1:5 for about 20 minutes, when the vapor
temperature reaches around 60°C and the Still temperature in the Reboiler is around
75°C at 175 mmHg. Then the reflux ratio was changed to 1:1. The vacuum was
maintained around 170-175 mmHg. Then start collecting the distillate in the receiver
till the vapor temperature reaches around 75 °C. Initially a fraction of water is distilled
out along with ketazine. This distillation is carried out till there is no ketazine in the
bottom product. The distillation is continued to remove the azeotrope of mixture
which was collected at a constant vacuum of 170-175 mmHg. After removing the
azeotrope the mixture is further treated at a vacuum of 170-175 mm Hg to
concentrate it to 80% HH which is obtained as bottom product.

EXAMPLE: PROCESS DESCRIPTION

REACTOR SECTION
Initially, MEK from tank-farm is fed to storage tank with a vent condenser 3811 kg of
MEK is added to a preparation vessel using pump.1230 kg Acetamide, 29 kg of
Ammonium Acetate and 15 kg of EDTA are fed from a conveyor under nitrogen
 13

blanket into a hopper and added to the preparation vessel. These solids are kept in
suspension and charged into the reactor by gravity in about half an hour. The
reactor is maintained at 25°C under atmospheric pressure. A vent condenser is
provided on the reactor with chilled water circulation to avoid loss of MEK during the
process.

Then H 202 is added to the reactor at 212 kg/hr from storage tank using pump and
simultaneously Ammonia gas is sparged into the reactor through a mass flow
controller at 110 kg/hr from a header connected to bullets. The reactor jacket is
provided with double limpet coil for circulation of hot water in HW limpet and chilled
water in CHW limpet. During the first 3 hrs of addition of H 202 and NH3, the
temperature of the reaction mixture is raised from 25°C to 50°C by circulating hot
water. Once the temperature reaches 50°C, Hot water is cut off while both H 202 &
NH3 additions continue. Since the reaction is exothermic, the mixture temperature
slowly rises to 58°C and it is maintained between 55°C-58°C by circulating chilled
water in CHW limpet while addition of H 202 & NH3 is continued. During the reaction
process, small amount of H 2O2 decomposes to water & oxygen, and most of the
Acetamide converts to Ammonium Acetate. After completion of H 202 addition i.e.
after approx. 5 hours, ammonia sparging is continued at the same flow rate for 1
more hour. The reactor is run till H 202 conc. in the product mixture is not greater
than 0.2 % which is achieved in almost 30 min after charging of NH 3 is discontinued.
The H2O2 conc. is tested by Titration method.

The reaction mixture is then allowed to cool to 25 °C by circulating chilled water. The
reaction mass obtained after 7 1/2 hrs (including charging and discharge time)
containing unreacted MEK, Ketazine, Ammonia, water, Ammonium Acetate,
Acetamide and some unknown compounds, is sent to a separator for layer
separation. When the amount of moisture in the organic layer is not greater than 3
%, the two layers (Organic and Aqueous) are separated and collected in two
different storage tanks. The moisture content is tested using Karl Fischer moisture
analysis method. The separation is completed in approx. 60 min. Ketazine yield
obtained after completion of reaction is not less than 85% with respect to H202.
 14

The gases formed during reaction process are sent to a scrubber where ammonical
liquor is collected and oxygen is let out to atmosphere. The ammonical liquor is
collected in a storage tank and sent to ammonical liquor tanker using pump.

AQUEOUS PROCESSING SECTION

The Aqueous Layer is taken into Batch Distillation/Dehydration Columns using pump
which is operated initially at 120°C for 3-3.5 hrs to expel ammonia, to evaporate
water in the feed and then at 140°C — 150 °C for dehydration of ammonium acetate
to recover acetamide. The total batch time is 12 hours.
During this process at about 90-100°C Ammonium Acetate decomposes to acetic
acid and ammonia. To convert acetic acid back to Ammonium acetate, Ammonia
gas is sparged into the column from Ammonia buffer tank. The top product
containing ammonia, water, traces of MEK and Ketazine is condensed through
condenser into. Uncondensed Ammonia in the top product is collected using roots
blower and sent to ammonia buffer tank. Condensed top product containing Water
with 1% ammonia, traces of MEK and Ketazine is collected in Storage tank. After 3-
3.5 h, reboiler temperature is increased to 140°C. At this temperature Ammonium
Acetate dehydrates to form Acetamide. Ammonia, water vaporizing are condensed
and collected into Storage tank. Uncondensed Ammonia in the top product is
collected using roots blower and sent to ammonia buffer tank. The dehydration
process is carried out only till concentration of acetamide reaches 70% is obtained in
the bottom product. The Bottom product is a homogenous mixture of Acetic Acid,
Acetamide, Ammonium Acetate and water.

This mixture is sent to crystallizer where it is first cooled to 60°C by circulating

cooling water in the jacket for one hour and then to 15°C using brine and maintained
at this temperature for 5 h. This crystallized product is sent to a centrifuge where
wet solids i.e., acetamide are separated and collected in bags for recycle.

The mother liquor obtained from the centrifuge containing water with Acetic Acid,
Ammonium Acetate, some Acetamide, is collected in storage tank and sent to Batch
Dehydration column using pump which is dedicated to mother liquor dehydration to
recover acetamide. The column is maintained at 140-150 °C and the batch time is 9
hrs. The top product containing water with 1% ammonia and acetic acid is
 15

condensed. Acetic acid is refluxed back to the column and ammonical liquor is
collected in storage tank. Bottom product containing Acetic Acid, Acetamide,
Ammonium Acetate and water is sent to crystallizer where it is first cooled to 60 °C
by circulating cooling water in the jacket for one hour and then to 15°C using brine
and maintained at this temperature for 5 hours. This crystallized product is sent to
centrifuge where wet solids are separated and collected in bags for recycle. Mother
liquor separated is collected in storage tank and sent for recycle.

ORGANIC LAYER PROCESSING SECTION

Organic layer from containing MEK, ketazine Mixture is taken into a continuous
distillation column operated at 200-250 mmHg and 60-70°C to remove MEK-water
azeotrope, and NH3. The condensed top product is collected in a storage tank. The
distillation column is operated such that moisture content in the bottom product is not
greater than 2 %. This is measured using Karl Fischer moisture analysis method.
This MEK is checked for conformance to the MEK specifications for reuse and
collected in a storage tank. The bottom product containing ketazine, acetamide,
some amount of MEK, unknown compounds is collected in a storage tank.

This mixture is then sent to a continuous counter current packed column where it is
water washed. Water is added to the column from top and the feed mixture is fed
from bottom. The Acetamide present in the feed is collected into the aqueous layer
along with traces of ketazine and MEK and collected as bottom product into a
storage tank. The top product i.e. the organic layer which is free from Acetamide is
collected into a storage tank.

This mixture containing ketazine, some amount of MEK, water, unknown compounds
is now fed into a distillation column which is operated at 80-85°C and 20-25 mmHg to
purify the ketazine. The condensed top product from condenser containing ketazine,
some amount of MEK, water and some unknown compounds is collected in a
storage tank for Hydrolysis. The bottom product containing unknown compounds,
some ketazine is collected in a storage tank and sent to a Evaporator to recover
ketazine as top product. The evaporator is operated at 80-85°C and 20-25 mmHg.
The Ketazine thus recovered from top through condenser is sent for hydrolysis. The
bottom heavies (Unknown compounds) from the evaporator are sent for incineration.
 16

HYDROLYSIS SECTION

Initially, Ketazine and DM water is then sent to static mixer where HH is also added.
The output pH of water coming from static mixer going to distillation column is
maintained at 8.2-8.5 by adjusting the quantity of HH added to water. The two
streams, ketazine, DM water are preheated passed through static mixer into reactive
distillation column.
Preparing the Reactive Distillation Column for first Run:
First, fill 50% of the column reboiler with 20% HH. Then, purge the column with
nitrogen for 20 minutes. Discontinue nitrogen purging, and heat the column slowly
using hot oil system. Once the column bottom temperature reaches 100 °C, vent out
the steam generated in the column which will also expel any trapped nitrogen. Close
the vent valves and continue heating. When the column bottom temperature
reaches 180°C, column pressure will be around 8.0 to 9.0 bar pressure. DM water
preheated to 70-80°C,is fed into the column through a static mixer. After the column
stabilizes at around 180°C & 10.0 bar pressure, start feeding Ketazine preheated to
70-80°C, in pre-heater into the column through the static mixer. Maintain 180-190°C
at the bottom and 160-165°C at the top of the column at a pressure of 10.5 to 11bar
thorough out the process.
The top product containing MEK, un-reacted water and soluble ketazine is
condensed in condensers are collected in a reflux drum. Ketazine and Water are
refluxed back into the column and MEK is separated. Bottom product containing 40%
H.H along with some methyl ethyl ketazine is collected in storage tank. This Crude
40% HH is sent to concentration to 80% HH.

PURIFICATION AND CONCENTRATION SECTION

Initially, a mixture of 40% HH, methyl ethyl ketazine, water, hydrazone and some
unknown compounds is fed into the reboiler of Batch Distillation Column from
storage tank. The column is run for 7hrs under a vacuum of 180 mmHg, at a
temperature of 65-70°C. The distillation is carried out till no methyl ethyl ketazine is
present in bottom product and it is measured using GC method. The top product
containing water, methyl ethyl ketazine is condensed and stored in storage tank.
This mixture is sent back for reactive distillation.
 17

The bottom product containing around 60-70% HH and water is collected in storage
tank and sent to a Continuous azeotropic Distillation Column where heavies are
separated. The column is maintained under a vacuum of 180 mmHg, at a
temperature of 65-70°C. The Column is operated such that 90% of the feed is
collected as top product. The top product containing 70% HH and balance water is
condensed and collected in storage tank. The bottom product containing HH, water
and solids is stored in a storage tank and sent to pressure leaf where the solids are
separated. The mother liquor is collected in storage tank and sent for recycle.

The top product is sent to a Continuous Distillation Column where 70% HH is

concentrated to 80% HH. The column is maintained under a vacuum of 180 mmHg,
at a temperature of 65-70°C. The percentage of HH in the bottom is 80% and is
measured using GC method. The bottom product containing 80%F1H, some water is
collected in storage tank. The top product containing about 30% HH and water is
condensed in condenser and collected in storage tank. This mixture is sent for
recycle.

ANALYTICAL METHODS
To determine the rate of formation of ketazine, it is necessary to estimate its amount
present in the reaction mixture. So a suitable analytic technique is the main
requirement for the accurate determination of the product. Methyl ethyl ketazine in
the reaction mixture have been estimated by using gas chromatography which gave
results of good accuracy. The organic layer was analyzed for the amount of methyl
ethyl ketazine and the aqueous layer was analyzed for the peroxide present.

RAW MATERIAL ANALYSIS

MEK Analysis

A Gas Chromatography method was used to analyze MEK. The GC conditions used
as follows:

Column TENAX TA, 2 m x 1/8" SS column

Oven Temp : Initial 70°C hold for 3min then rise to 250°C
@ 15°C/min
 18

Injection port Temp : 230°C

Carrier gas Flow : 15 ml/min (H2)

Sample size : 0.2 pL

Quantification : External area normalization technique

Acetamide Analysis

The pure substance of Acetamide is dissolved in methanol and analyzed by GC

method. The area for the pure acetamide is calculated and used to quantify the
acetamide content in feed sample. The 70% solution of acetamide dissolved in water
as feed is analyzed by injecting into GC without methanol. The quantification of
acetamide content is calculated using the formula.

% Acetamide = ( A sampie / Apure) x 100

Asample Area count for acetamide in sample from GC

Apure = Area count for acetamide in Pure from GC

The GC conditions are same as mentioned above.

Intermediate Analysis

Nature of the process requires two layers of samples always to be analyzed. One is
organic layer and the other one is aqueous layer. In addition to that, analysis of the
samples collected during the process of concentrating organic layer and removal of
acetamide from aqueous layer and at various stages of process as and when
required, is also to be done. All these samples were analyzed by GC method using
the following conditions.

Column : TENAX TA, 2 m x 1/8" SS column

Oven Temp : Initial 70°C hold for 3 min then rose to

250°C @ 15°C/min.

Injection port Temp. : 230 °C

Carrier gas Flow : 15 ml/min (H2)

 19

Sample size : 0.2 pi

Quantification : External area normalization technique

Analysis of Hydrogen Peroxide

Hydrogen peroxide in the reaction mixture was estimated by titrating against

standard KMnO4 solution. 0.1 N KMnO 4 solution is used for this purpose. The
procedure for carrying out titrations has been taken from worksheets of Solvay
Specialty Chemicals Limit.

Reagents Used

In the Peroxide Analysis, following chemicals are used

Standard KMnO4 solution (0.1 N)

Conc.H 2SO4 (A.R. Grade)

Sodium Oxalate (Na 2C2O4) (A.R. Grade)

Distilled Water

Reaction Involved

The reaction between hydrogen peroxide and potassium permanganate can be

represented a follows

5 H 202 + 2 KMnO4 + 3 H2SO4 _ _ + 2 MnSO 4 4' 5 02 + 8 H2O

K_2SO

The net ionic equation is

+2
5 H202 + 2 Mr104- + 6 11± , 2 Mn + 5 02 + 8 H2O

Preparation of 0.1 N KMnO 4 Solutions

Molecular Weight of KMnO 4 = 158.04 g

Equivalent Weight ofKMnO4 = Molecular Weight of KMnO4 / Valency

158.04/5 = 31.608 g

For making 1 N KMnO 4 solution, we have to dissolve 31.608 grams of KMnO 4 in 1 L

of Distilled water. Thus for making 0.1 N KMnO 4 solution, we have to dissolve 3.1608
 20

g of KMnO 4 in 1 liter i.e. 1000 ml of distilled water. This KMnO 4 solution formed is
thus stored in amber colored bottles to protect from photo degradation.

Principle
2 moles ofKMnO 4 reacts with 5 moles of H202.

Molecular Weight of H202 34.002 g

Molecular Weight of KMnO 4 = 158.04 g

Thus 2 x 158.04 g of KMnO 4 reacts with 5 x 34.002 g of H 2 0 2 Now; 1 L of 0.1 N

KMnO 4 solutions contains 3.1608 g of KMnO 4 . And thus 1 ml of 0.IN KMnO 4 solution
contains 3.1608/1 000 g of KMnO 4 . Thus 1 ml of 0.1 N KMnO 4 is required to titrate.

[{(5x34.002) / (2 x 158.04)} x (3.1608/1000)] g of H202.

= or 1 ml of 0.1 N KMnO 4 x 1.7001 x 10 -3 g of H202.

Standardization of KMnO4 Solution

Potassium permanganate is standardized by its reaction with sodium oxalate,
Na 2 C 2 O 4 . For this purpose, take about 0.3g of dry sodium oxalate in 500 ml iodine
flask. This sodium oxalate had been dried in oven at 105°C for 4 h and after cooling
is kept in a desiccator with calcium chloride to avoid any moisture absorption. To this
sodium oxalate add 20 ml of distilled water and 5 ml of cone. H 2 SO 4 . Now start
adding KMn0 4 solution, prepared as per the procedure given, from a 50 ml burette
until the first appearance of faint pink color that persists for 30 seconds. Note the
volume of KMnO 4 consumed (V i ) for the titration. In this titration, temperature of the
solution rises on the addition of cone. H 2 SO 4 . The temperature of the solution in the
flask should not fall below 70°C before the end point is reached. The reaction
involved is as follows:

5 Na2 C 2 0 4 + 2 KMnO4 + 8H 2 SO 4 2 MnSO4 + K 2 SO 4 + 5Na2 SO 4 + 100O 2 + 8H20

The net ionic equation is

5C2 0 4 2- + 2 Mn04 - + 16H + —*2Mn-2 + 10 CO2 + 8H20

Hydrogen peroxide analysis calculations

To find out the amount of peroxide present in the given sample take about 0.2- 0.3
 21

(W2) g of H 202 in a 250 ml iodine flask. To this add 20 ml of distilled water and then
add 5 ml of Concentrated H 2SO4 (A.R. Grade) carefully. Titrate the solution against
standard KMnO4 solution till a light pink color persists for 30 seconds. Note the
volume of KMnO4 consumed (V2) for the titration.

1 ml of 0.1 N KMnO4 x 1.7001x1 0"3

1 ml of 1 N KMnO4 x 1.7001x10-2

When,

V2 = Volume of KMnO 4 used (ml)

N = Normality of KMnO 4 solution.

W2 = Weight of sample taken for analysis (g).

V2 x N x 1.7011 x 10 -2 x 100
H202 =

W2

Product Analysis

The final product obtained is Hydrazine Hydrate which is also analyzed using GC
with following conditions:

Column : TENAX TA, 2m x 1/8" SS column

Oven Temp : Initial 70°C, hold for 3 min, then raise to

250°C @ 15°C/min

Injection port Temp : 230 °C

Carrier gas Flow 15 ml/min (H2)

Sample size : 0.2 pl

Quantification : External area normalization technique

 22

SIGNIFICANCE OF THE WORK CARRIED OUT

In view of the importance and lack of efficient scalable production methods for the
preparation of hydrazine hydrate, the present process developed by us serves as a
highly energy efficient, clean, eco-friendly and scalable method for the production
of concentrated aqueous solutions of hydrazine hydrate. This method also serves
as a catalyst free approach for the hydrolysis of ketazine to produce hydrazine
hydrate.

ADVANTAGES OF THE INVENTION

The various advantages of the present invention are given below:
The main advantage of the present invention is that it provides an energy
efficient, clean, eco-friendly and scalable process for the production of
concentrated aqueous solutions of hydrazine hydrate.
The advantage of the present invention is that the process employs recyclable
solid crystalline acetamide as the catalyst, unlike the known methods wherein,
the catalyst solutions are used.
Another advantage of the present invention is the employment of simple
reaction and operational parameters.
Purification and/or recovery of the products and/or by products form at all the
stages of the process is straight forward.
This process involves catalyst free hydrolysis of ketazine to give hydrazine
hydrate with lower ratio of water to ketazine (1:1.5), unlike the known
methods, where a catalyst and higher water ratio is required for hydrolysis.
This is an attractive and economic method for the production of concentrated
aqueous solutions of hydrazine hydrate.
WE CLAIM
1. A process for the preparation of aqueous solutions of hydrazine
hydrate comprising:
reacting hydrogen peroxide, ammonia, and ketone to form an azine in
presence of an activator selected from acetamide and ammonium acetate;
separating the resulting mixture from step (a) into a ketazine layer and a
aqueous solution layer;
concentration of ketazine and recovery of methyl ethyl ketone by evaporation;
purification of ketazine by vaccum distillation;
recovery of acetamide from aqueous layer by dehydration;
then returning the recovered methyl ethyl ketone and acetamide to step (a);
hydrolysis of the ketazine to obtain hydrazine hydrate and regenerating
the methyl ethyl ketone;
and recycling the methyl ethyl ketone to the stage (a),
(i) concentration and purification of hydrazine hydrate in stage (g) to obtain
40-80% of hydrazine hydrate.
2. The process as claimed in claim1, wherein the acetamide recovered from
dehydration stage (e) is further purified by centrifugation or filtration under
vaccum to get crystalline solid.
The process as claimed in claim 1, wherein the hydrogen peroxide is a 50 to
70 weight % H 202 solution.
The process as claimed in claim 1, wherein the molar ratio of hydrogen
peroxide: methyl ethyl ketone: and ammonia is 1:4:3.
The process as claimed in claim 1, wherein stage (a) is carried out at
temperatures ranging of 0° C to 60° C.
The process as claimed in claim 1, wherein stage (c) evaporation is carried
out at temperatures ranging from 85° C to 110° C.
7. The process as claimed in claim 1, wherein stage (d) vaccum distillation is
carried out at temperatures ranging from 75 ° C to 100° C, preferably
between 80° C -90° C.
 The process as claimed in claim 1, wherein the ratio of ketazine: water in
hydrolysis stage (g) is 18:12.
The process as claimed in claim 1, wherein the hydrolysis stage (g) is carried
out under a pressure ranging from 2 to 20 bars, preferably between 8 to 12
bars, and temperature ranging from 150° C to 200° C, preferably between
175° C to 200° C.

Dated this g day ofAI/ 2016

/Di Sll,!ATI\ St\NITANI

Soen'tist
TivF k;. n
r
LC,SIR)

1v1Jrg, NUN Deiht-110067

14,
 25
eft -
PROCESS FLOW DIAGRAM
-rold No . eff 4-0A -1

Dated theq day of ARM 2016.

aL oaLL:
Scientist
Innovation Protection Unit (IPU)
Council of Scientific & Industrial Research
 26

ABSTRACT

AN IMPROVED PROCESS FOR PRODUCTION OF HYDRAZINE HYDRATE

An improved process for the production of concentrated aqueous solutions of

hydrazine hydrate by ketazine method is described. In particular, it describes
preparation of hydrazine hydrate by ketazine method using 50-70% hydrogen
peroxide, recyclable solid acetamide and ammonium acetate activator for ketazine
formation and catalyst free hydrolysis of ketazine to give aqueous solutions of
hydrazine hydrate in energy efficient manner.