Raschig-phenol process

Raschig-phenol process is a phenol production process named after German

chemist Friedrich Raschig 1. This process combines 2 partial stages which are
oxychlorination of benzene to form monochlorobenzene followed by hydrolysis of
that monochlorobenzene produced. Process is divided into 2 stages to make the
products separation easier using simple fractional distillation 2.

Block diagram

Reaction

Interaction of benzene, hydrocholic acid and oxygen at the first stage process
might produce dichlorobenzenes, trichloro-benzenes, tetrachlorobenzenes,
pentachlorobenzene and hexachlorobenzene as a by-product 2. These by-
products are not presented in reaction as they are unwanted by-product and
can be separated easily by simple fractional distillation as by-products have
considerably high boiling point than chlorobenzene and steam 2.

Reaction pathways Temperatu Pressure H298 K /

re/ C kJ kmol-1
Benzene + hydrochloric acid + oxygen 250 (unknow -
Chlorobenzene + steam n) 0.07137

+ H-Cl + 0.5
+
Chlorobenzene + water Phenol + 425 (unknow 0.01760
Hydrogen chloride n)

+
+ H-Cl

Process route descriptions

First stage
- Benzene is converted into monochlorobenzene by oxychlorination reaction
using hydrochloric acid and oxygen over a CuCl2/ FeCl3 catalyst [2].
- By-products might be produced as well during reaction, such as
dichlorobenzenes, trichloro-benzenes, tetrachlorobenzenes,
pentachlorobenzene, hexachlorobenzene.
- Purification of monochlorobenzene need to be done using simple fractional
distillation and then condensed it to form liquid monochlorobenzene [2].
Second stage
- Hydrolysis catalyst of monochlorobenzene into phenol and hydrogen
chloride in which eventually hydrogen chloride is recycled to the first stage
[2]
.
- Separation of this hydrolysis products can be separated easily using
simple fraction distillation as the by-products has higher boiling point
reinforced by the fact that no azeotropes believed to be found in the
product stream.

However, this method is found impractical as very high purity needed in

separation of chemical. Plus, dichlorobenzene impurities come from chlorination
of benzene in the first stage mixed with monochlorobenzene will contaminate the
phenol product with other organic chlorine compounds produced by hydrolysis [2].
This situation resulting a formation of an azeotrope in which simple fractional
distillation cannot be used anymore [2].

Safety and Environment

Benzene is classified as a hazardous chemical species. There is no environmental

effect form benzene as it is assumed to be completely react but safety
precautions has to be taken care of during the reaction. There are quite
hazardous specifications relating benzene :
- Flammable. Benzene is a very flammable in both liquid and gas phases. As
we are dealing with the high temperature, this has to be in our concern 3.
- Irritating, can cause harmful to the nervous system besides irritate nose
and throat once being inhaled. A proper clothes as to put on once dealing
with the benzene to avoid contacting the skin. A protective goggles also
has to be worn to avoid direct contact to the eye 3.
Hydrochloric acid is a corrosive chemical as it is a categorized as a corrosive
substances. Direct contact of acid on skin and eyes must be prevented using
appropriate protective equipment such as goggles and proper clothes. As an
acid-possessed properties, hydrochloric acid is very corrosive when in contact
with something made up with metal or limestone 4. This risk is lowered by
recycling back the hydrogen chloride produced in the second stage to the first
stage process.
 Sustainability

Benzene is one of the largest commodity production category. Benzene can be

obtained from the combustion process of organic waste, wood, etc. It is also
widely produced in petroleum refinery as well as in soil where usually from the
industrial discharge containing benzene 5. However, benzene is considered to be
a sustain raw material as it is also can be produced in many alternative ways.
Another way to obtain benzene is from by-product of disproportionation of
toluene where xylene isomers is made up and also by dehydrogenation of
naphthenes using a catalyst 6. Hydrochloric acid is extremely used in industrial
as it is a sustain chemical that easily to be prepared. Firstly, chlorine gas is react
with hydrogen gas to produced hydrogen chloride gas. Then, hydrogen chloride
produced is dissolved in water and forming hydrochloric acid 7. Air is use
alternately rather than compressing the air to get pure oxygen because is it quite
costly to do that compressing 8.

Economic potential

Benzene Hydrochloric Oxygen Phenol

acid
Moles (kmol) 1 1 0.5 1
Molar Mass (kg/kmol) 78.11 36.46 16.00 94.11
Mass (kg) 78.11 36.46 8.00 94.11
Unit Price ($/kg) 1.20 0.0085 - 1.5442
Price ($) 93.73 0.31 - 145.32
Total ($) 94.04 145.32
EP ($/kmol Benzene) 51.28
EP ($/kmol Phenol) 51.28
EP ($/kg Phenol) 0.54

Calculation of mass
= *

= 1 78.11

= 78.11

Calculation of price
=

= 0.07811 * 1200

= $ 93.73

Calculation of economic potential ( $ kmol -1 Benzene )

= 145.32 94.04

= $ 51.28 kmol-1 Benzene

Calculation of economic potential ( $ kmol -1 Phenol )

 $ per kmol Benzene
= Moles of phenol

$ 51.28
= 1

= $ 51.28 kmol-1 Phenol

Calculation of economic potential ( $ kg-1 Phenol )

$ per kmol Phenol

= Molar mass of phenol

$ 51.28
= 94.11

= $ 0.54 kg-1 Phenol

Calculation of heat of reaction of stage 1

Ho(reaction) = Hof(products) - Hof(reactants)

Ho(reaction) = [+52.0 + (-241.83) + 0] [+48.7 -167.16]

Ho(reaction) = -71.37 kJ mol-1

References
1 "RaschigHooker Process". En.wikipedia.org. N.p., 2017. Web. 2 Feb. 2017. Retrieved from
https://en.wikipedia.org/wiki/Raschig%E2%80%93Hooker_process

2 "Patent US3221063 - Distillation In Raschig-Phenol Process". Google Books. N.p., 2017.

Web. 2 Feb. 2017. Retrieved from
https://www.google.com/patents/US3221063

3 N.p., 2017. Web. 2 Feb. 2017. Retrieved from

https://www.ccohs.ca/oshanswers/chemicals/chem_profiles/benzene.html

4 "Pollutant Fact Sheet". Apps.sepa.org.uk. N.p., 2017. Web. 2 Feb. 2017. Retrieved from
http://apps.sepa.org.uk/spripa/Pages/SubstanceInformation.aspx?pid=5

5 "Impact Of Water Pollution On Human Health And Environmental Sustainability". Google

Books. N.p., 2017. Web. 2 Feb. 2017. Retrieved from
https://books.google.co.uk/books?
id=MdvdCgAAQBAJ&pg=PA38&lpg=PA38&dq=sustainability+of+benzene
&source=bl&ots=g0h853yBiK&sig=SzagpNcPNNriIxUZHcH96cQ1kB0&hl=
 en&sa=X&ved=0ahUKEwiQ38qctO_RAhVoKsAKHbWnC7YQ6AEIRjAI#v=on
epage&q=sustainability%20of%20benzene&f=false

6 martin,. "5 Methods Of Preparing Benzene". Slideshare.net. N.p., 2017. Web. 2 Feb. 2017.
Retrieved from
http://www.slideshare.net/bejoybj/5-methods-of-preparing-benzene

7 "Reagantchemical". Reagentchemical.com. N.p., 2017. Web. 2 Feb. 2017. Retrieved from

http://www.reagentchemical.com/production-methods.html

8 Process Synthesis handbook 2016 by Megan Jobson and Jie Lie.