University of Diyala

College of Engineering
Chemical Engineering Department

Production of formaldehyde
A project report Submitted to the Engineering Department
of Chemical of the University of Diyala in a partial fulfillment
for the Degree of B.Sc in Chemical Engineering

By

Sajad jabar sabty

Muhanad asaad adham

Mohammad abdulljalel mudhafar

Supervisor:
Assist. prof. Dr. ahmed daham waheeb

2015 - 2016
‫ك َما‬ ‫َّ‬ ‫ع‬‫و‬ ‫ة‬‫كم‬‫ِ‬
‫احل‬
‫و‬ ‫اب‬ ‫ت‬ ‫ِ‬
‫يك الكَ َ َ َ َ َ َ َ َ‬
‫م‬ ‫ل‬ ‫( … َوأَ َنزَل اهللُ َعلَ َ‬

‫يك َع ِظيماً )‬‫َ‬‫ل‬ ‫ع‬ ‫ِ‬

‫ضل اهلل َ َ‬
‫ُ‬ ‫َ‬‫ف‬ ‫ن‬
‫َ‬ ‫ا‬ ‫ك‬
‫َ‬‫و‬ ‫م‬
‫َُ‬ ‫ل‬
‫َ‬ ‫ع‬‫ت‬
‫َ‬ ‫ن‬‫ك‬‫ُ‬ ‫ت‬
‫َ‬ ‫َل‬
‫َ‬

‫صدق اهلل العظيم‬

‫سورة النساء (‪) ١١٣‬‬

‫‪2‬‬
 Dedication

To my beloved family . . . .
My parents .. My Father & My Mother
My Brothers
My Sisters

To my lovely friends . . . .

sajad,muhanad,Mohammed

3
 Table of Contents
Chapter one ……………………………………………………….. 1
1- Summary ……………………………………………………..... 2
1.1 - Introduction …………………………………………………...2
1.2 - Health effects …………………………………………………3
1.3 - Sources ………………………………………………………. 3
1.4 - Demand ……………………………………………………… 3
1.5 - Use of formaldehyde ……….………………………………...4

1.6- Physical and chemical properties ……………………………..4

1.6.1- Physical Properties of Formaldehyde ………………………4

1.6.2 - Chemical properties ………………………………………...5

1.7- Production methods …………………………………………...6

1.7.1- From methanol by silver catalysts process ………………….8

1.7.2- Metal oxide catalyst process ………………………………..10

1.7.3- Production of formaldehyde from other hydrocarbon gases ..12

1.8- Selection of process ……………………………………….…..13

Chapter two ……………………………………………………….14

2.1-Mass balance ……………………………………………….…..15

2.1.1- First run mass balance………………………………………..15

2.1.1.1- Material balance on the reactor ……………………………15

2.1.1.2- Material balance on the absorber…………………………...18

2.1.1.3- Material balance on the distillation column…………………22

2.1.2- Second run mass balance ……………………………………..25

4
2.1.2.1- Mass balance on the reactor ……………………………….25

2.1.2.2- Mass balance on the absorber……………………………...26

2.1.2.3- Mass balance on the distillation column …………………..27

2.2- Energy balance ………………………………………………...29

2.2.1- Mixing point between streams 2 , 3 and 15 …………………29

2.2.2- Energy balance on the heat exchanger E-101 ……………….30

2.2.3- Energy balance on the heat exchanger E-102 ……………….32

2.2.4- Mixing point between streams 6, 7 ………………………….33

2.2.5- Energy balance on the reactor ……………………………….33

2.2.6- Energy balance on the heat exchanger inside the reactor ……34

2.2.7- Energy balance on the absorber ……………………………...36

2.2.8 - Energy balance on the heat exchanger E-103………………...37

2.2.9- Energy balance on the distillation column T-101 …………….38

2.2.10- Mixing point of stream 17 , 18 and 19………………………40

2.2.11- Energy balance on the heat exchanger E – 106……………..42

Chapter three ………………………………………………………43

3.1- Introduction of design …………………………………………44

3.2- Reactor design………………………………………………….44

3.2.1- Reactor design equation ……………………………………..44

3.2.2 Mole balance …………………………………………………45

3.2.3 Net rate laws ………………………………………………....46

3.2.4 Rate laws …………………………………………………….46

3.2.5- Stoichiometry ……………………………………………….48

5
3.2.6- Combination ………………………………………………..49

3.2.7- Pressure drop ……………………………………………….50

3.2.8 – Result ……………………………………………………...52

3.3- Packed-bed absorber design…………………………………..56

3.3.1- Introduction ……………………………………………….56

3.3.2 -Packing material…………………….………………………56

3.3.3- Sizing of packed tower……………………………………..56

3.3.3.1- Packed tower diameter …………….……………………..57

3.3.3.2 - Packing height (Z packing) ……….…………………….60

3.4 - Distillation column design …………….…………………...61

3.4.1 – Introduction ………………………….……………………61

3.4.2 – From material balance ……………………………………62

3.4.3 – Calculation number of plates ……………………………..63

3.4.4 – Column height …………………………………………..67

3.4.5 – Column diameter ………………………………………..67

Chapter four …………………………………………………….73

Control loop system on absorber …………………………………74

Chapter five ……………………………………………………..75

5.1- Safety & environment precaution ………………………….76

5.1.1- Methanol ………………………………………………….76

5.1.1.1- Exposure ………………………………………………..76

5.1.1.2- Reactivity ……………………………………………….77

5.1.1.3- Storage…………………………………………………..77

6
5.1.2-Formaldehyde ……………………………………………77

5.1.2.1- Fire hazards ……………………………………………78

5.1.2.2-Exposure ……………………………………………….78

5.1.2.3-Storage …………………………………………………78

5.2- Plant location ……………………………………………...78

5.2.1- Introduction……...………………………………………78

5.2.2 - CH2O plant location …………………………………...79

Chapter six …….………………………………………………80

6.1 – Introduction ………………………………………………81

6.2 – Raw material ……………………………………………..81

6.3 - Operating labor cost ………………………………………82

6.4- Equipment cost …………………………………………….83

Conclusion ……………………………………………………...84

Reference………..………………………………………………85

7
CHAPTER ONE
SUMMARY

8
1. Summary

1.1- Introduction

Formaldehyde is called Methyl aldehyde or Methylene glycol or Methylene

oxide it is a colorless, flammable gas or liquid that has a pungent, suffocating
odor. It is a volatile organic compound, which is an organic compound that
easily becomes a vapor or gas. It is also naturally produced in small, harmless
amounts in the human body. The chemical symbol for formaldehyde is CH2O.

Formaldehyde is released into the air by burning wood, kerosene, or natural gas;
from automobiles and diesel exhaust; and from cigarettes and other products. It
is found in the air at home, at work, and outdoors, especially in smog. It is also
found in some foods.

Formaldehyde occurs in forest fires, animal wastes, microbial products of

biological systems, and plant volatiles. It can also be formed in seawater by
photochemical processes .

Formaldehyde was discovered in 1859 by a Russian chemist named Aleksandr

Butlerov. Then in 1869, it was ultimately identified by the German chemist
August Hofmann. The manufacture of formaldehyde started in the beginnings of
the twentieth century. Between 1958 and 1968, the annual growth rate for
formaldehyde production averaged to 11.7%. In the mid-1970s, the production
was 54% of capacity. Annual growth rate of formaldehyde was 2.7% per year
from 1988 to 1997. In 1992, formaldehyde ranked 22nd among the top 50
chemicals produced in the United States. The total annual formaldehyde
capacity in 1998 was estimated by 11.3 billion pounds. Since then and the
production capacity around the globe is expanding exponentially reaching a
world’s production of 32.5 million metric tons by 2012. Due to its relatively low
costs compared to other materials, and its receptivity for reaching high purities,
formaldehyde is considered one of the most widely demanded and manufactured
materials in the world. It is also the center of many chemical researches and
alternative manufacture methods. This also explains the vast number of
applications of this material including a building block for other organic
compounds, photographing washing, glues, adhesives, paints, explosives,
disinfecting, tissue preservation and drug testing. formaldehyde is most
commonly produced in industry through the vapor- phase oxidation reaction
between methanol and air (Oxygen).

9
1.2- Health effects

The most probable route of human exposure to formaldehyde is inhalation .Non-

Cancer: Vapors are highly irritating to the eye and respiratory track. Acute
effects include nausea, headaches, and difficulty breathing. Formaldehyde can
also induce or exacerbate asthma, and throat irritation and Repeated exposure to
it cause skin irritation

1.3- Sources

Formaldehyde is both directly emitted into the atmosphere and formed in the
atmosphere as a result of photochemical oxidation of reactive organic gases in
polluted atmospheres containing ozone and nitrogen oxides. Photochemical
oxidation is the largest source (could be as high as 88 percent) of formaldehyde
concentrations in California ambient air. A primary source of formaldehyde is
vehicular exhaust Formaldehyde is a product of incomplete combustion. About
9 percent of direct formaldehyde emissions are estimated to come from the
combustion of fossil fuels mobile sources.

The primary stationary sources that have reported emissions of formaldehydeare

crude petroleum and natural gas extraction, manufacturers of miscellaneous
nonmetallic mineral products, and gas production and distribution services.

1.4- Demand

Demand for formaldehyde will grow with the development of the manufacturing
sector mainly the chemical industries such as disinfectants, cosmetics,
pharmaceuticals, insecticide & fungicides and the like. The demand for the
output of such establishments is in turn influenced by population growth,
urbanization, income rise and expansion of health services and the like.
Considering the combined effect of the above factors a growth rate of 10% is
taken to forecast the future demand.
PROJECTED DEMAND FOR FORMALDEHYDE (KG)

Year Projected
Demand
2012 143,000
2013 157,300
2014 173,030
2015 190,333
2016 209,366

10
1.5- Use of formaldehyde

Formaldehyde is an important industrial chemical because of its versatility as a

chemical intermediate (Gerberich et al. 1994). It primarily is used in the
production of urea-formaldehyde, phenol-formaldehyde, and melamine-
formaldehyde resins, which are used as adhesives in the production of particle
board, fiber board, and plywood. Formaldehyde is also used in the manufacture
of plastics, insulation, fertilizers, fungicides, biocides, corrosion inhibitors,
embalming fluids, disinfectants, and household cleaners, and it is used in the
textile industry .

1.6- Physical and chemical properties

Formaldehyde is a flammable, colorless gas at room temperature and has a

pungent, suffocating odor (Budavari et al. 1989). Odor thresholds ranging from
0.5 to 1.0 parts per million (ppm) (ATSDR 1999) and 0.06 to 0.5 ppm
(Gerberich et al. 1994) have been reported. Formaldehyde reacts readily with
many substances and polymerizes easily, making it one of the world's most
important industrial Compound. (Gerberich et al. 1994). Selected chemical and
physical properties are listed in TABLE

1.6.1- Physical Properties of Formaldehyde

Properties Formic aldehyde, methanal, methyl aldehyde,

methylene oxide, Oxo methane, ox methylene
CAS registry number 50-00-0
Molecular formula HCHO
Molecular weight 30.03
Boiling point –19.5°C
Melting point –92°C
Flash point 83°C (closed cup)
Explosive limits 7% to 73%
Specific gravity 1.067 with respect to air
Vapor pressure 3,890 mmHg at 25°C
Solubility Very soluble in water; soluble in alcohol and ether
Conversion factors 1 ppm = 1.23 mg/m3; 1 mg/m3 = 0.81 ppm
Vapor Pressure 3284 mm Hg at 20 0C
Vapor Density 1.03 for aq. soln.; 1.08 for gas
Density/Specific Gravity 1.067 (air = 1)
Log Octanol/Water 0.35
Partition Coefficient
Conversion Factor 1 ppm = 1.23 mg/m3

11
1.6.2 - Chemical properties

Formaldehyde is one of the most reactive organic compounds known. The

various chemical properties are as follows:

Decomposition
At 150 ºC formaldehyde undergoes heterogeneous decomposition to form
methanol and CO2mainly. Above 350 ºC it tends to decompose in to CO and H2.

Polymerization
Gaseous formaldehyde polymerizes slowly at temperatures below 100 ºC,
polymerization accelerated by traces of polar impurities such as acids, alkalis
orwater. In water solution formaldehyde hydrates to methylene glycol
H
H2C=O + H2O HO C OH
H
Which in turn polymerizes to polymethylene glycols, HO (CH2O)nH, also called
polyoxy methylenes.

Reduction and Oxidation

Formaldehyde is readily reduced to methanol with hydrogen over many
metaland metal oxide catalysts. It is oxidized to formic acid or CO 2 and H2O.In
the presence of strong alkalis or when heated in the presence of acids
formaldehyde undergoes cannizzaro reaction with formation of methanol and
formic acid. In presence of aluminum or magnesium methylate,
paraformaldehyde reacts to form methyl formate (Tishchenko reaction)
2HCHO HCOOCH3

Addition reactions
The formation of sparingly water-soluble formaldehyde bisulphite is an
important addition reaction. Hydrocyanic acid reacts with formaldehyde to give
glyconitrile.
HCHO + HCN HOCH2 - C  - N

Resin formation
Formaldehyde condenses with urea, melamine, urethanes, cyanamide, aromatic
sulfonamides and amines, and phenols to give wide range of resins.

12
Chemical reaction of Formaldehyde

Number Reaction ΔHR,973 K(kJ/mol)

(1) CH3OH +1/2O2 → HCHO+H2O -156
(2) CH3OH →HCHO+H2 +85
(3) CH2O → CO+H2 +12
(4) CH3OH+2/3O2→CO2+2H2O −676
(5) CH2O+O2 → CO2+H2O −519
(6) CH2O+1/2O2→CH2O2 −314
(7) CH3OH → C+H2O+H2 −31
(8) CO+H2⇄ C+H2O −136

(9) CO+H2O ⇄ CO2+H2 −35

1.7- Production methods

Today two main processes are in use for the production of formaldehyde from
methanol, the silver process and the oxide process. The first can be divided in to
two processes, the methanol ballast process and the BASF Badische Anilin&
Soda-Fabrik process as shown in Figure 1.1.

Methanol
ballast
process
Silver
Process
Processes for
BASF
Production of
Process
Formaldehyde Oxide
Process

Figure 1.1. The different process types for production of formaldehyde from
methanol.

13
Figure 2.2. schematic overview of the silver process. The dashed square shows
what only exist in the methanol ballast process

Figure 2.3. A schematic scheme over the oxidation process (Table 1.1.)
]%[ Methanol BASF Oxide
Ballast
Conversion 77-88 97-98 95 – 98
Yield mol. 86-90 89.5-90.5 <92.5
Formaldehyde [wt] 42 40-55 <55
Methanol in product <1 < 1.3 0.5-1.5
[wt]

14
1.7.1- From methanol by silver catalysts process
Feed mixture of pure methanol vapor and blown in air is generated in evaporator
the mixture combined with steam and enter the reactor vapor passes through bed
to silver catalyst or silver gauze. The conversion is in completed and the reaction
takes place in 600-720 °C the reaction gases cooled in directly with water, the
remaining heat of bottom of a formaldehyde absorption column. In the water
cooled section of column, the bulk of a methanol, water, and formaldehyde
separate out a 42% formaldehyde solution from the bottom absorption column is
fed to distillation column, methanol recovered at top of column, and recycled to
the bottom of evaporator A formaldehyde and less than l%( wt) methanol
product containing up 5 is taken from, the bottom of distillation column and
cooled. Diagram(1) explains the process:

DIAGRAM 1

15
FORMALIN (FOLRMALDEHYDE 37 WT. % SOLUTION)

Flash point 64 °C

Autoignition temperature 430 °C

Explosive limits 36%
Lower Explosion Limit 6%
Upper Explosion Limit 36%
Products of Combustion Carbon monoxide (CO) and Carbon

16
1.7.2- Metal Oxide Catalyst Process

The Formax process developed by Reichhold chemicals to produce

formaldehyde through direct catalytic oxidation of methanol and some other 7
by-products such as carbon monoxide and dimethyl ether forms In 1921, the
oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was
introduced to and patented. Then in 1933, the iron-molybdenum oxide catalyst
was also patented and used till the early 1990’s. Improvements to the metal
oxide catalyst were done through the metal composition, inert carriers and
preparation methods. The first commercial plant for the production of
formaldehyde using the iron-molybdenum oxide catalyst was put into action in
1952. Unlike the silver based catalyst in this project, the iron-molybdenum
oxide catalyst makes formaldehyde from the exothermic reaction (1) entirely.
Under atmospheric pressure and 250 –350 ºC, methanol conversion inside the
reactor could reach 99% and a yield of 88% - 92%.

17
The process begins by mixing of vaporized methanol and air prior to entering
the reactors. Inside the heat exchanger reactor, the feed is passed through the
metal oxide catalyst filled tubes where heat is removed from the exothermic
reaction to the outside of the tubes. Short tubes (1 – 1.5 m) and a shell diameter
2.5 m is the expected design of typical reactors. The bottom product leaving the
reactors is cooled and passed to the absorber. The composition of formaldehyde
in the absorber outlet is controlled by the amount of water addition. An almost
methanol-free product can be achieved on this process design. The advantage of
this process over the silver based catalyst is the absence of the distillation
column to separate unreacted methanol and formaldehyde product. It also has a
life span of 12 to 18 months, larger than the sliver catalyst.

18
1.7.3- Production of formaldehyde from methane and other hydrocarbon
gases

Another method of producing formaldehyde is through the oxidation of

hydrocarbon gases. An increase in the amount produced of formaldehyde is
expected in this process. However, the hydrocarbon formaldehyde is usually
obtained as dilute solution which is not economically concentrated accompanied
by other aldehydes and by-products. However, improvements have been effected
by the use of special catalysts and better methods of control. Wheeler
demonstrated that methane is not oxidized at an appreciable rate below 600°C.
The difficulty in this method is in controlling the oxidation of reaction. Ethylene,
ethane and propane oxidations can be controlled to yield formaldehyde und er
similar conditions to methane. Higher hydrocarbon gases can be oxidized at much
lower temperatures than methane and ethane. These methods have been described
by Bibb also reported by Wiezevich and Frolich, who used iron, nickel,
aluminum, and other metals as catalysts and employed pressures up to 135
atmospheres. The Cities Service Oil Company has developed a commercial
process using this method.

19
1.8- Selection of process

The oxide process has to think about how to let out their tail gas, which mostly
consist of nitrogen, oxygen ,CO and other compounds from the absorption tower
such as formaldehyde and methanol exist in the tail gas. Because of these
compounds the tail gas cannot be released into the air as it is, compared to the
silver processes that can let their tail gas go without consideration.
the disadvantage of The oxide process design is the need for significantly large
equipment to accommodate the increased flow of gases (3 times larger) compared
to the original silver catalyst process design. This increase in equipment sizing
clashes with economic prospect behind the design costs.
silver catalysts process

In this project formaldehyde is to be produced through a catalytic vapor-phase

oxidation reaction involving methanol and oxygen according to the following
reactions.
CH3OH + ½ O2 HCHO + H2O (1)
CH3OH HCHO + H2 (2)

The desired reaction is the first which is exothermic with a selectivity of 9,

while the second is an endothermic reaction. Operate of the process at
atmospheric pressure and very high temperatures (600°C – 650°C) .

20
 CHAPTER TWO
MATERAIL AND ENERGY BALANCE

21