OXIDATION

Oxidation Agents:
1) Air -21 vol% O2.
-Free & abundant availability
-P.P/conc. Decreases as reaction progresses .Hence, low
driving force and subsequent low reaction rate
-Large size Reactor.
-O2/N2 non condensable gases .Hence, down stream
processing/separation more difficult. Large size down stream
equipment.
2) Pure Oxygen-a) Pressure swing Adsorption.
b) Air liquefaction/Fractionation.
Cost of O2 much more than air.
But -lower size reactor
-Smaller size downstream processing/
separation units.
3) Nascent Oxygen:

a) 2KMnO4 + 3H2SO4 ---------- K2SO4 + 2MnSO4 + 3H20 + 5[O]

b) K2Cr2O7 + 4H2SO4 ----------- K2SO4 + Cr2(SO4)3 + 4H2O + 3[0]
Both creates environmental problems
KMnO4 –color tinge difficult to remove in ppm level also.
c) NaOCl + H20 ---------------- NaOH + HOCl
Hypo chloride HOCl--------- HCl + [O]
d) NaClO2 + ½ Cl2 -------------- NaCl + ClO2
Chlorite ClO2 ------------- ½ Cl2 + 2[O]
e) NaClO3 ------------------------ NaClO2 + [O]
Chlorate
c,d,e-all end up with chloride in solution which is corrosive & environmental
problem.
f) H2O2 --------------------------- H2O +[O]
g) O3-------------------------------- O2 + [O]
No by products or H2O –which is harmless to environment. Part of Green
chemistry..Favored oxidizing agents.
5) Dehydration, oxygen introduction and destruction of carbon
linkage:
C10H8 + 4.5O2 ------------ C8H4O3 + 2H2O + 2CO2
i.e. oxidation of naphthalene to phthalic anhydride.

6) Per oxidation occurs under certain conditions:

C6H5CH(CH3)2 ------------ C6H5(CH3)2COOH
Cumene or Cumene Hydro peroxide
isopropyl benzene
 Vent

Compressed Air Chilled water*

CWR CWS
Acetaldehyde
Acetic
Manganese acid
Acetate as Product
catalyst

Dilute
Acetaldehyde
to Distillation
column

ST

CON

Crude Acetic Acid

Air pressure -4-5 bar Bottom
Reaction Temp< 60ºC Discharge
Reaction time- 10-12 hrs

Acetaldehyde is low boiling substance, hence, chilled water use in scrubber is must.
 Formaldehyde from Methanol
Catalyst : Silver Or Copper Guaze.
Temperature : 450-600ºC
CH3OH : O2 :: 1 to 0.3
1 to 0.5
Recycle methanol : 15 % of feed.
Yield : 85-90%

a) Advantage of using chilled water.

b) Interchange exchanger operation.
c) Light end stripper-
i. Absorbing MeOH/Formaldehyde.
ii. Separating light end products.
Catalyst activity is controlled to maintain a balance between the endothermic
dehydrogenation & exothermic oxidation reactions at reaction conditions of 450-600C.Some
complete combustion takes place. The compromise finds 4-5% CO+CO2 in the reactor tail gas.
 Phenol
a) Per oxidation:
C6H5-CH(CH3)2 + O2 -------------- C6H5-C00H(CH3)2

i. Fresh Cumene + recycled(hydrogenated) Cumene 1:4 –mixed

ii. Reaction temperature 100 – 130ºC
iii. pH : 8.5 – 10.5.

b) Hydrolysis:
C6H5-COOH(CH3)2 + aqH2SO4 ----- C6H5OH + (CH3)2CO

i. Aq.H2SO4 strength 10-25%

ii. Reaction temp 55-65ºC
iii. Acid is recycled
iv. Product stream is water washed to remove adhering acid.
v. Product range-very wide: Acetone -56.5,Phenol-181.4,Cumene-152.5,Methyl styrene-164
vi. Product stream contains 76% Cumene,14% Phenol,8% Acetone and 1-2% α-methyl styrene
and acetophenone.
vii. M.P of phenol- 42-43ºC
Quantitative requirements:
a) Basis :1 tons of phenol(92% yield) + 0.6 ton acetone
Cumene :1.40 tons
Air : 1.53 tons
Small quantities of sulfuric acid and emulsifying agents
Co product : Acetone
b) Plant capacities: 50-125 tons/day

Process Description:
Cumene (isopropyl benzene) made by alkylation of benzene with
propylene is mixed with recycle Cumene(1:4) and sent to the
hydrogenate. Unsaturates and α-methyl styrene are converted to
saturated materials to avoid undesirable decomposition of the
peroxide during the oxidation step. Hydrogen over nickel catalyst at
100º C in a batch reactor is the usual process for purification.
oxidation is carried out in the presence of air in an aqueous
emulsion stabilized by an alkali such as sodium carbonate in the 8.5-
10.5 pH range. Vent gases are passed through a condenser to recover
hydrocarbons.
 Phthalic Anhydride
a) Naphthalene oxidation:
V2O5,400ºC

C10H8 + 4½ O2 --------------- C6H4(CO)2O + 2CO2 + 2H20 ∆H= -426kcal

b) O-Xylene Oxidation:
V2O5,400ºC

C6H5(CH3)2 + 3O2 --------------- C6H10(CO)2O + 3H20

Major side reactions –complete combustion (15-20%)

C10H8 + 12O2(air) ------------ 10CO2 + 4H2O
C8H10 + 10½O2(air) ------------ 8CO2 + 4H20

Minor side reactions:

C10H8 + 9O2(air) ----------- C4H2O3 + 6CO2 + 3H20
C8H10 + 7½O2 (air) -------- C4H2O3 (Maleic Anhydride)

Phthalic Anhydride- B.P-295ºC

M.P-131ºC
 Fixed Bed Fluid Bed

Temperature, ºC 380-450 520-600

Contact time, µC 0.1-0.4 10

Air / Feed 22.6 15

Yield 75-80 75-80

Maleic Anhydride Yes No

 Crystallization and separation

Mother liquor
1st Cut
Pure PNCB( C.B- 82-82.5ºC) 60% ,m

Reaction
mass Crystallization Vacuum 2nd Cut
p-65% and Distillation Rich in ,p
o-34% separation
m-1%

3rd Cut
crude ,o
Mother
liquor
65-66%,o Residue

Crystallization
and separation

Pure O
C.P-31.5-32ºC