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15.4

CMT 650 CASE STUDY

GREEN CHEMISTRY IN CHEMICAL PROCESS/TECHNOLOGY
INNOVATION IN PRODUCTION OF HYDRAZINE
GROUP 2

NAME STUDENT GROUP

ID
MOHAMMAD AL-FATEH BIN MOHD SOFIAN 2020597935 RAS2456C

MOHD NAJIBULLAH BIN ABDUL RASHID 2020970377 RAS2456C

MUHAMMAD AMIR AIMAN BIN SAPIHUDIN 2020993181 RAS2456C

MOHAMAD HAFIZIE BIN ABD KUDUS 2020978705 RAS2456C

NUR IZZAH AFIFAH BT AZHAR 2019207212 RAS2456A

PREPARED FOR
Dr. Saifulddin Bin Azami
 ACKNOWLEDGEMENT

First and foremost, we would like to praise and thank the Almighty God for giving us the

strength and because of His blessing, we finally managed to accomplish this assignment. Without

His blessing, we wouldn’t have gone his far. This assignment cannot complete without effort and

cooperation from our group members, which consist of Muhammad Al-Fateh bin Mohd Sofian,

Mohd Najibullah bin Abdul Rashid, Muhammad Amir Aiman bin Sapihudin, Nur Izzah Afifah

binti Azhar, and Mohamad Hafizie bin Abd Kudus. We always work hard to produce a good

assignment with our full commitment and responsibility.

Therefore, we would like to acknowledge with thank our lecturer Dr. Mohammad

Saifulddin bin Mohd Azami because without his guidance our assignment cannot been done

properly like this. He always gives us support and guidance on how to do our assignments in

purpose to produce a good outcome. He inspired us greatly to work on this project. We also like

to thank him for teaching us in this course.

Finally, we would like to express our thankfulness to Universiti Teknologi MARA

Cawangan Perlis Kampus Perlis for allowing us to conduct this writing report assignment and an

honorable mention goes to our friends for the support.

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Table of Contents
ACKNOWLEDGEMENT ii
EXECUTIVE SUMMARY iv
1.0 INTRODUCTION 1
2.0 FINDINGS 3
2.1 PROBLEMS 3
2.1 .1 ISSUES IN PRODUCTION OF HYDRAZINE BY RASCHIG METHOD 3
2.1 .2 ISSUES IN PRODUCTION OF HYDRAZINE BY UREA METHOD 5
3.0 DISCUSSION 7
3.1 Ketazine Method 7
3.2 Hydrogen peroxide method 8
4.0 CONCLUSION 10
RECOMMENDATIONS 11

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 EXECUTIVE SUMMARY

Hydrazine is a critical chemical in our society, whether for organic synthesis or energy use. The

direct conversion of NH3 to hydrazine is appealing, but it remains a difficult task because hydrazine

degradation is thermodynamically more feasible than NH3 NH bond cleavage. As a result, any

catalyst that can activate NH3 will unavoidably decompose N2H4. We show how the Raschig and

Urea method contains hazardous chemical reactions and how innovation was required to

advantageously prevent thermal degradation, a recurring issue with previous technologies such as

the Ketazine and Hydrogen Peroxide methods. This research also points to a method for

scavenging OH radicals by varying the NH3 concentration.

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1.0 INTRODUCTION

Hydrazines are reactive compounds and their derivatization may be needed for better

analysis. The reactivity of hydrazines toward aldehydes has been used for their derivatization for

HPLC analysis. For most uses, hydrazine is produced as hydrazine hydrate in a formulation with

water. The hydrate may be produced commercially by three methods which is the Raschig process,

the ketazine process, and the peroxide process. In the Raschig process, the original commercial

production process for hydrazine involves oxidation of ammonia to chloramine with sodium

hypochlorite, then the further reaction of the chloramine with excess ammonia and sodium

hydroxide to produce an aqueous solution of hydrazine with sodium chloride as a by-product.

Fractional distillation of the product yields hydrazine hydrate solutions. Currently, most

hydrazine is produced by the ketazine process, which is a variation of the Raschig process.

Ammonia is oxidized by chlorine or chloramine in the presence of an aliphatic ketone, usually

acetone. The resulting ketazine is then hydrolyzed to hydrazine. In the peroxide process, hydrogen

peroxide is used to oxidize ammonia in the presence of a ketone. Anhydrous hydrazine is the

formulation used in rocket fuels and is produced by dehydration of the hydrate by azeotropic

distillation with aniline as an auxiliary fluid. Hydrazine (anhydrous or hydrate) has numerous

commercial uses.

The principal current use for hydrazine is as an intermediate in the production of

agricultural chemicals such as maleic hydrazide. It is also used as an intermediate in the

manufacture of chemical blowing agents which are used in the production of plastics such as vinyl

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flooring and automotive foam cushioning, as a corrosion inhibitor and water treatment agent, as a

rocket propellant, and, as a lesser extent, as a reducing agent, in nuclear fuel reprocessing, as a

polymerization catalyst, as a scavenger for gases, and several other uses. It has also been used as

a medication for sickle cell disease and cancer.

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2.0 FINDINGS

2.1 PROBLEMS

2.1 .1 ISSUES IN PRODUCTION OF HYDRAZINE BY RASCHIG METHOD

The Raschig method was the primary method used to produce hydrazine hydrate abroad in the

1960s. In industrial manufacturing, this method was first applied in 1906. When NaClO and NH3

were combined, hydrazine hydrate was created. The following is the reaction equation:

NaClO+NH2Cl+ NH3 + NaOH → NH2NH2 + NaCl+ H2O

NaOH made up 8% of the total mass employed in the reaction. Pure water was used to absorb NH3

into an aqueous solution when C-12 was added to create NaClO since there was excess NaOH.

NH3 and NaClO solution are mixed in a 20:1 mass ratio with a 170°C reaction temperature limit.

Under pressure, the reaction can be completed in a matter of seconds. Gelatin is added to the

reaction system to assist raise the yield. The distillate in the reaction tower also contains certain

by-products, unreacted ammonia, NaCl, and NaOH in addition to hydrazine hydrate. The bottom

liquid enters the evaporation tower after being flash evaporated under normal pressure, separating

the ammonia and bottom liquid through the ammonia separation tower. After sodium chloride and

sodium hydroxide are separated, the water is discharged from the top of the tower, and on the

bottom obtained hydrazine hydrate. The process flow is as follows:

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 Raschig process flow diagram（adapted from Dai 2008.）

The Raschig process contains fatal flaws despite being established and trustworthy, the raw

components being easily accessible, and the cost being somewhat low. The yield of hydrazine is

quite low since it can be oxidised and destroyed by chloramine. Only 65% of the total process is

yielded, which results in high product costs and excessive raw material use. Lows levels of

hydrazine which is between 3% and 4% are present in the reaction solution, and salts like sodium

chloride and ammonium chloride are produced with significant evaporation and high energy

requirements. Ammonia that is produced in excess must be recovered in big quantities, which

raises equipment and operational expenses. The Raschig process uses less raw materials than the

urea approach, but it costs more to buy the equipment and uses more energy.

The overall cost is less than the urea method when the production scale is huge. FBC Company in

1974, the United States Unirol (u-nroyal) and Fairmont, France PCUK, and other companies in

1981 abolished this method.

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2.1.2 ISSUES IN PRODUCTION OF HYDRAZINE BY UREA METHOD

The Schestakof method is another name for the urea method. At the start of the Industrial

Revolution, French chemists proposed the Raschig method for producing hydrazine from urea.

The reaction of urea method's equation is as follows:

NH2 CONH2 + NaOH + 2NaOH → NH2 NH2 + NaCl + NaCO3 + H2 O

NH2 Cl+ NH3 + NaOH →NH2 NH2 + NaCl+ H2 O

This is a Hofmann amide degradation reaction. This reaction involves a hydrogen atom on

a nitrogen atom. To form N-chloramide, an atom in the urea molecule (carbonamide) is replaced

by chlorine. When alkali reacts with N-chloramide, hydrogen chloride is lost and an intermediate

with six valences is formed. This intermediate is referred to as azene. Because of its structure, an

arene is a very active reaction intermediate that can participate in a variety of reactions at the same

time (Burenin 2000). Because azene has a very short lifetime, it is usually produced during the

reaction and then the next step of the reaction is carried out. It rearranges under the action of alkali

to form an isocyanate, which is hydrolyzed to form hydrazine hydrate and salt.

The urea process is basically an improved Raschig process that uses urea instead of

ammonia. The process does not have the issue of large-scale nitrogen reactant circulation. First,

Cl2 and NaOH react to form a NaClO solution, followed by urea and NaClO. To obtain the finished

product, the NaOH solution is oxidized with oxidants such as KMnO4 and H2O2, then evaporated,

desalted, and refined.

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 The method is mature and the process is simple. When MgSO4 is used as the catalyst, the

reaction takes 1 to 2 minutes, the temperature quickly rises to 100°C, and the yield is

approximately 70% (Mhlaba et al., 2019). This method substitutes urea for ammonia, which

simplifies equipment and reduces investment. However, because the reactant NaClO is a strong

oxidizer and the product is a strong reducer.

Because the side effects are so severe, spraying accidents are possible when ingredients or

improper operations are used. As a result, the yield of the urea oxidation method is low, typically

70 to 80 percent. To prevent side effects, keep the hydrazine concentration as low as possible

(generally 2 percent to 3 percent by mass) (Hoanvu et al., 2021). The by-product salt and alkali

content are 12 times that of hydrazine. Soda ash is recovered through freezing crystallisation and

evaporated while being stirred (5-layer tank). Because medium desalination and subsequent

distillation to concentrate hydrazine require a significant amount of heat and mechanical energy,

there are constraints such as high energy consumption, high raw material costs, and environmental

concerns.

The goal of recent process improvements has been to reduce side effects and increase

hydrazine hydrate yield. Gelatin, protein glue, KMnO4, and MnSO4 can all be added to the reaction

medium. The most common in China are KMnO4 and MnSO4. However, when dissolved in urea

solution, these two additives turn a dark red color, which is difficult to control in practice.

Simultaneously, MnO2 is produced by the reaction of manganese salt, which causes fouling and

even blockage of pipelines, potentially causing environmental pollution. Instead of manganese

salt, MgSO4 additives are now used.

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3.0 DISCUSSION

3.1 Ketazine Method

The German Coal Mining Association affiliate Bergbau-Farschung was the first to patent

the ketazine method, also known as the Bergbau-Bayer-Whifel method, which was later refined

by the parent companies Bayer and Huifen. Industrialization started in the 1970s, and research

started in the early 1960s. The Raschig method has been enhanced by this one. The difference is

that acetone is added to the reaction solution, causing the active hydrazine produced by the reaction

to immediately combine with acetone to form a less active acetone azine. Under specific

conditions, the acetone azine is hydrolyzed to regenerate hydrazine and acetone (Kaur et al., 2010).

Ammonia is oxidized with NaClO in the presence of aliphatic ketones to produce

hydrazone, azine, or isohydrazone. The pH of the system, the ratio of ketones, and the reaction

circumstances all affect the product's composition. Hydrazone and isohydrazone can both be

transformed to ketazine when there is an excess of ketone present. The intermediate is condensed

and hydrolyzed into hydrazine and hydrazine salt when the oxidant has been entirely consumed.

At a pressure of 4 MPa and a temperature of 140 °C, a hydrazine hydrate solution is created using

ammonia water and NaClO solution. Air stripping is used to remove extra ammonia before

evaporative desalting and rectification are carried out to produce the final product, hydrazine

hydrate (Sridhar et al., 2003).

Ammonia and ketones can be recovered and recycled using this technique. The CaCl2

waste brine is treated with Na2CO3 to produce Ca2CO3, which is subsequently precipitated and

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transformed into Ca (OH)2 by high temperature calcining and water dissolution, and finally

recycled. This approach, therefore, provides the benefits of a high rate of raw material use and low

byproducts.

The creation of the intermediate product ketazine is a distinctive feature of this process.

Ketazine's ability to resist additional oxidation entirely overcomes the drawbacks of hydrazine

being broken down and lost during the Raschig process, leading to a revolutionary boost in yield.

Since the concentration of the reaction product may be increased and the amount of hydrazine in

the dilute hydrazine solution produced by hydrolysis can be increased to more than 10%, the

comparatively stable ketazine reduces the amount of evaporation, concentration, and energy

consumption (Wang 2021).

3.2 Hydrogen peroxide method

Early in the 1980s, French PCUK (also known as the PCUK technique) successfully

developed the hydrogen peroxide method and constructed an industrial facility. The plant’s

capacity has increased to 12,000 tonnes per year so far. The facility has had numerous renamings

and ownership changes. This approach was also created by the Japanese MGC firm, which also

produced a tool. The current device’s annual tonnage capacity is 12,000 tonnes. There are two

main responses to this technique. One method produces ketazine (also known as azine) by

oxidizing NH3 with H2O2 in the presence of methyl ethyl ketone and a catalyst; the other method

involves hydrolyzing the latter to produce hydrazine hydrate and methyl ethyl ketone, with the

ketone being recycled.

Instead of adding hydrazine directly during the synthesis process, ketones are added to

produce intermediate ketazine, which can prevent the hydrazine (reducing agent) from interacting

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with the oxidizing agent and being consumed, increasing the yield. Because its ketazine is almost

insoluble in water, methyl ethyl ketone is frequently employed in industry. After the reaction, a

straightforward standing sedimentation method can be used to separate the ketazine from the

aqueous media. A larger concentration of hydrogen peroxide should be employed to generate a

higher ketazine solution concentration; its mass fraction is typically 70%. The hydrolysis process

has two steps and can be stopped at any time. The hydrolysis is frequently carried out in a

rectification tower, and the produced ketone is promptly eliminated, to upset the balance and

ensure that the hydrolysis reaction goes smoothly.

The relative costs of chlorine and NaOH play a major role in the economic comparison of

the hydrogen peroxide technique, the Raschig method, and the ketazine method. If there is a cheap

source of H2O2, this approach is highly appealing because it has a yield of 75%. While the methyl

ethyl ketone used in this process is more expensive than acetone, the resulting ketone azine is not

water-soluble, is simple to separate, and does not require rectifying, therefore this approach

requires less energy than the ketazine method. The hydrogen peroxide process has the advantages

of producing no salt by-products, no environmental contamination, and less extra ammonia. Phase

separation operation is used in nitrogen recovery, which requires less energy than alternative

procedures and produces products of higher quality. By substituting H2O2 for chlorine, many

issues, including corrosion and pollution brought on by chlorine and NaCl, are avoided (Wang,

2021).

Although the hydrogen peroxide method is still in its infancy, it still has numerous

drawbacks, such as the hydrolysis process in the rectification tower requiring a lot of energy. The

hydrolysis tower’s hydrazine hydrate solution has a relatively low concentration (up to 40 %). The

hydrolysis process is also affected by a variety of other elements, which makes industrial

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production unpredictable and makes it difficult to produce on a larger scale (the current maximum

production scale is 12,000 tons/year). However, due to catalyst and separation difficulties, the

catalytic distillation hydrolysis process has not been industrialized even though it has been

successful in limited experiments (Wang, 2021)

4.0 CONCLUSION

In a conclusion, the production of hydrazine by the Raschig method and Urea method give

few drawbacks. In the Raschig method, a large amount of excess ammonia needs to be recovered,

and equipment and operating costs increase. Compared with the urea method, the Raschig method

has lower raw material costs, but the equipment investment and energy consumption are higher.

The urea method has been eliminated in foreign countries, but the urea method is still the main

production method to produce hydrazine hydrate in China. Hence, the Ketazine method and

Hydrogen peroxide method are used to prepare hydrazine. The advantages of the hydrogen

peroxide method are no environmental pollution, and less excess ammonia. Nitrogen recovery uses

phase separation operation, energy consumption is lower than other methods, and product quality

is improved. Another important advantage of this method is to replace chlorine with H2O2, to avoid

a series of problems such as corrosion and pollution caused by chlorine and NaCl.

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RECOMMENDATIONS

The hydrogen peroxide method will ultimately replace the urea method in the manufacturing of

hydrazine since it has the most advantages in terms of environmental protection, product quality,

and cost. The law of progress in the modern world can only be satisfied by phasing out antiquated

production technology as soon as feasible and implementing cutting-edge technology to raise the

general level of production equipment. The position of hydrazine hydrate is also becoming more

indispensable due to the rise in demand for it. Chemical compounds with less nitrogen and

phosphorus can be employed as raw materials in the synthesis of hydrazine hydrate to lessen the

wastewater generated during manufacture.

The Raschig method, the urea method, the ketazine method, and the hydrogen peroxide

method are the four processes used to make hydrazine hydrate. The methods that use a lot of energy

and produce more pollutants should be changed and improved as science and technology advance

and environmental protection ideas gain popularity. Although there are many different methods

for treating wastewater at the moment, not all of them are effective, and others still require

research. Using the nanofiltration membrane technology as an example, there are still several

issues with membrane manufacture and cleaning that need to be addressed.

The level of living for people has increased steadily in recent years because to the ongoing

advancement of science and technology. The resulting environmental issues, however, have also

consistently caught people's attention. Global warming brought on by excessive carbon dioxide

emissions and energy depletion brought on by over usage of fossil fuels are now issues that people

must deal with. The topic of the current era is the development of clean energy as well as the

logical development and use of resources to achieve sustainable developme

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Sridhar, S., Srinivasan, T., Virendra, U., & Khan, A. A. (2003). Pervaporation of ketazine
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Wang, D. (2021). Wastewater treatment in hydrazine hydrate production.

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