PROCESS PLANT SIMULATION LABORATORY

REPORT ON

PRODUCTION OF DIMETHYL SULFOXIDE FROM LIGNIN

SUBMISSION TO

Prof. Hara Mohan Jena

Submitted By:

Roll No: 113CH0098 Neelathi Venkata Sravanthi

113CH0099 Thimirishetty Swetha

113CH0100 Sadi Tanusha

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INTRODUCTION:
Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula (CH3)2SO. This
color-less liquid is an important polar-aprotic solvent that dissolves both polar and
nonpolar compounds and is miscible in a wide range of organic solvents as well as water. It
has a relatively high melting point. DMSO has the unusual property that many individuals
perceive a garlic-like taste in the mouth after contact with the skin.

This process concerns the production of dimethyl sulfoxide (DMSO) from lignin, a polymer
that occurs naturally in wood. DMSO is an important polar aprotic solvent useful in many
segments of industry. Dimethyl sulphide is used primarily as an odorant in natural and
manufactured gas. It is also an intermediate in preparing many S-containing derivatives
including dimethyl sulfoxide. This latter chemical has unique chemical solvent properties,
acting as a catalyst also in solution reactions. It has found increasing uses as a solvent for
spinning synthetic fibres such as poly-acrylonitrile.

R-Stoic

When the reaction stoichiometry is known but information on kinetics is not available RStoic
is used. The block must have one or more feed streams, one required output stream. Optional
connections are the water decant and input and output heat streams. Two specifications must
be made either to the outlet stream conditions or the heat duty of the reactor. Multiple
reactions can be defined in the Reactions form. Heat of reaction will be calculated based on
the reaction of 1 mole of a reference component (reactant). The temperature, pressure, and
phase for the calculations must be specified.

R-equilibrium

When one or more reactions involved are equilibrium reaction, the R-equil block can be used.
The block requires knowledge of the reaction stoichiometry, and performs chemical and
phase equilibrium reactions. The R-equil block has a vapour and liquid phase product streams
(both are required). The only required information for this block is the output stream and the
reaction. With this input, all the required calculations are made based on thermodynamics
calculations.

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AIM:

To prepare dimethyl sulfoxide from lignin using aspen plus.

BLOCKS INVOLVED IN SIMULATION:

DMS reactor
Methyl Mercaptan scrubber
DMS column
DMSO reactor
DMSO column

The kraft process (also known as kraft pulping or sulfate process) is a process for conversion
of wood into wood pulp, which consists of almost pure cellulose fibres, the main component
of paper. The kraft process entails treatment of wood chips with a hot mixture of
water, sodium hydroxide, and sodium sulphide, known as white liquor, that breaks the bonds
that link lignin, hemicellulose, and cellulose. The technology entails several steps, both
mechanical and chemical. It is the dominant method for producing paper

PROCESS:

Sulfate pulp black liquor was concentrated to 45 50% solids and then pumped to a
high pressure reactor along with molten sulfur. Steam was sprayed in the reactor to
raise the temperature up to 2300C.
Demethylation of liquor occurs via reaction with the sulfur to form dimethyl sulfide
(DMS) and methyl mercaptan (MM).Then reaction mass was charged to flash tank
where sulfur-containing products was removed overhead while the demethylated
black liquor was returned to the pulp mill for digestion chemicals.
Using 10%caustic washings, mercaptan and remaining water was removed in MM
scrubber and returned to the pulp plant.
The overheads from the scrubber was washed with 50% caustic and then run to the
DMS column where dimethyl sulfide was purified by distillation
To produce dimethyl sulfoxide (DMSO), the DMS was line-blended with nitrogen
tetra oxide (N2O4) and fed into the bottom of the liquid-phase oxidation reactor
(DMSO reactor) where, the oxidation of DMS was carried out using nitrogen tetra
oxide and converted into the dimethyl sulfoxide. The oxygen is added to reoxidize
the nitrogen oxide.
The washed liquid mixture was run into the evaporator where the overhead was sent
to the DMSO column for final purification.
In DMSO column, dimethyl sulfoxide was separated from water.

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DMS Reactor

Components used:
Sulphur
Methyl-para-Toluate
Methyl Mercaptan
Dimethyl Sulphide
Water
Sulphur dioxide
Para-Toluic acid

Method used: Peng Robinson

Streams used:
Lignin
Specifications:
Temperature : 200 C
Pressure: 2 atm
Methyl-para-Toluate : 100 kg/hr
Water : 100 kg/hr

Sulphur
Specifications:
Temperature : 200 C
Pressure: 2 atm
Sulphur : 250 kg/hr

FLOW SHEET:

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 Blocks:
DMS reactor used: R-equilibrium
Specifications:
Temperature: 230 C
Pressure: 35 atm
Phase: Vapor-liquid
Reaction:
3S + 3 C9H10O2 + 2H2O ---------> C8H8O2 + (CH3)2S + CH3SH + SO2

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 Convergence:
Maximum iterations: 30
Error Tolerance: 0.0001

Results:

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DMS COLUMN:

Components used:
Methyl Mercaptan
Dimethyl Sulphide
Water

Method used: Peng Robinson

Streams used:
Feed
Specifications:
Temperature : 35 C
Pressure: 1 atm
Methyl Mercaptan : 20 kg/hr
Dimethyl Sulphide : 40 kg/hr
Water : 40 kg/hr

Flow sheet:

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Results:

DMSO Reactor : Rstoic

Components used:
Dimethyl sulphide
Nitrogen Tetroxide
Oxygen
Dimethyl sulfoxide
Nitric oxide
Water

Method used: Peng Robinson

Streams used:
5% DMS
Specifications:
Temperature : 40 C
Pressure: 1 atm
DMS: 100 Kmol/hr

N2O4
Specifications:
Temperature : 30 C
Pressure: 1 atm
N2O4 : 55 Kmol/hr
Oxygen

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 Specifications:
Temperature : 35 C
Pressure: 1 atm
O2 : 80 Kmol/hr

Flow sheet:

Block:

DMSO reactor: Rstoic

Temperature: 37 C
Pressure: 1 atm
Phase: Vapour liquid free water

Reactions:
CH3S +N2O4 --------> 2CH3S=O +2NO
2NO + O2 ----- N2O4

Results:

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DMSO COLUMN:

Components used:
Dimethyl Sulfoxide
Water

Method used: Peng Robinson

Streams used:
Feed
Specifications:
Temperature : 50 C
Pressure: 1 atm
Dimethyl sulfoxide: 60 kmol/hr
Water: 40 kmol/hr

Flowsheet:

Column:

Type: equilibrium
Number of stages: 5
Valid phases: Vapor-liquid
Distillate rate: 0.5 kmol/hr
Reflux ratio: 10

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Results:

Flowsheet:

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 d m so p r e p a r a tio n
Str e a m ID 1 0 NAOH BT MP R-2 BT MP RD 1 BT MP RD 3 CO OL WT R CR DDMS O DM S DM S,MM DM SO L IG NIN N2 O4 O2 ON L YDM S SU L P HU R WA TER WT RVP R
F ro m DM SCOL MN DM SREC TR MM SCRU BB DM SORC TR DM SCOL MN DM SREC TR DM SOCL MN MM SCRU BB DM SORC TR DM SOCL MN
To MM SCRU BB DM SORC TR DM SOCL MN DM SORC TR MM SCRU BB DM SREC TR DM SORC TR DM SORC TR DM SCOL MN DM SREC TR
P h a se L IQ UID MIX ED MIS SING L IQ UID L IQ UID VA P OR MIX ED MIX ED L IQ UID MIX ED VA P OR VA P OR VA P OR L IQ UID MIS SING VA P OR
Su b stre a m : M IXED
Mo le F lo w k m o l/hr
S 0 .0 6 .5 3 4 6 2 E-3 0 .0 2 4 .8 6 9 3 1 0 .0 .1 2 4 1 5 7 8 .1 2 4 1 5 7 8 2 5 .0 0 0 0 0 .1 2 4 1 5 7 8 0 .0 0 .0 0 .0 .1 3 0 6 9 2 4 1 2 0 .0 0 0 0 0 .0 1 .1 9 0 5 E -4 9
MM 0 .0 1 .5 5 5 0 7 8 0 .0 .5 6 5 1 0 3 4 0 .0 2 9 .5 4 6 4 9 2 9 .5 4 6 4 9 3 1 .6 6 6 6 7 2 9 .5 4 6 4 9 0 .0 0 .0 0 .0 3 1 .1 0 1 5 6 0 .0 0 .0 1 .7 9 6 1 E -2 0
D MS 0 .0 1 .5 3 2 4 1 8 0 .0 1 .0 1 8 2 9 7 0 .0 2 .9 1 1 5 9 5 2 9 .1 1 5 9 5 3 1 .6 6 6 6 7 2 .9 1 1 5 9 5 0 .0 0 .0 0 .0 3 0 .6 4 8 3 7 0 .0 0 .0 2 .0 6 6 3 E -2 2

S O2 0 .0 1 .5 6 9 8 5 8 0 .0 .2 6 9 5 1 1 4 0 .0 2 9 .8 2 7 3 0 2 9 .8 2 7 3 0 3 1 .6 6 6 6 7 2 9 .8 2 7 3 0 0 .0 0 .0 0 .0 3 1 .3 9 7 1 6 0 .0 0 .0 4 .4 7 5 8 E -2 1
P -TOL - 0 1 0 .0 .2 0 0 6 9 8 2 0 .0 9 0 .9 8 6 0 4 0 .0 3 .8 1 3 2 6 5 3 .8 1 3 2 6 5 9 5 .0 0 0 0 0 3 .8 1 3 2 6 5 0 .0 0 .0 0 .0 4 .0 1 3 9 6 3 0 .0 0 .0 2 .6 4 1 6 E -4 8
H 2O 1 0 0 .0 0 0 0 1 .7 2 5 4 9 6 0 .0 1 0 2 .1 5 6 7 2 5 0 .0 0 0 0 2 8 2 .7 8 4 4 3 2 .7 8 4 4 2 3 6 .6 6 6 6 7 2 8 2 .7 8 4 4 1 0 0 .0 0 0 0 0 .0 0 .0 3 4 .5 0 9 9 2 0 .0 0 .0 1 .1 7 0 0 E -3 0
O2 0 .0 0 .0 0 .0 0 .0 0 .0 7 8 .2 0 8 0 4 0 .0 0 .0 7 7 .2 0 8 0 4 0 .0 0 .0 9 0 .0 0 0 0 0 0 .0 0 .0 0 .0 1 .0 0 0 0 0 0
N 2 O4 0 .0 0 .0 0 .0 0 .0 0 .0 9 8 .6 8 9 7 8 0 .0 0 .0 9 8 .6 8 9 7 8 0 .0 1 0 0 .0 0 0 0 0 .0 0 .0 0 .0 0 .0 1 .6 4 4 8 E -3 1

D MSO 0 .0 0 .0 0 .0 0 .0 0 .0 2 6 .2 0 4 3 6 0 .0 0 .0 2 6 .2 0 4 3 6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 1 .0 8 8 0 E -3 9
NO 0 .0 0 .0 0 .0 0 .0 0 .0 2 .6 2 0 4 3 6 0 .0 0 .0 2 .6 2 0 4 3 6 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 3 .4 3 0 2 6 E-8
M ETHY -0 1 0 .0 .0 9 9 2 9 6 5 0 .0 3 .0 1 4 0 7 0 0 .0 1 .8 8 6 6 3 4 1 .8 8 6 6 3 4 5 .0 0 0 0 0 0 1 .8 8 6 6 3 4 1 0 0 .0 0 0 0 0 .0 0 .0 1 .9 8 5 9 3 0 0 .0 0 .0 3 .1 5 4 5 E -3 3
N AOH 1 0 .0 0 0 0 01 .3 5 5 1 E -7 3 0 .0 1 0 .0 0 0 0 0 0 .0 0 .0 2 .5 7 4 7 E -7 2 0 .0 0 .0 0 .0 0 .0 0 .0 2 .7 1 0 2 E -7 2 0 .0 0 .0 0 .0
To ta l F l o w k m o l/hr 1 1 0 .0 0 0 0 6 .6 8 9 3 8 0 0 .0 2 3 2 .8 7 9 1 2 5 0 .0 0 0 0 5 5 6 .6 1 6 5 1 2 7 .0 9 8 2 2 5 6 .6 6 6 7 5 5 5 .6 1 6 5 2 0 0 .0 0 0 0 1 0 0 .0 0 0 0 9 0 .0 0 0 0 0 1 3 3 .7 8 7 6 1 2 0 .0 0 0 0 0 .0 1 .0 0 0 0 0 0

To ta l F l o w k g /hr 2 2 0 1 .4 9 9 3 4 4 .1 3 5 3 0 .0 1 5 9 8 5 .9 6 4 5 0 3 .8 2 0 2 3 1 2 3 .3 9 6 5 3 8 .5 7 1 2 0 6 6 7 .1 7 2 3 0 9 1 .3 9 1 6 8 1 9 .2 5 9 2 0 1 .1 0 8 2 8 7 9 .8 9 2 6 8 8 2 .7 0 7 3 8 4 7 .9 2 0 0 .0 3 1 .9 9 8 8 0
To ta l F l o w l/m in 3 5 .3 9 4 0 0 3 9 9 5 .2 4 6 0 .0 2 2 3 .7 4 1 3 7 4 .4 4 4 8 37 .8 1 8 0 1 E+5 7 5 9 0 9 .6 7 7 8 9 .0 1 1 7 2 8 7 .8 7 2 9 4 6 9 5 8 .4 3 4 0 9 0 0 .1 8 3 7 8 9 7 .3 2 7 9 9 0 4 .9 1 3 3 .0 1 9 8 6 0 .0 1 2 3 .7 2 3 6
Te m p e r a ture C 2 9 .0 0 0 0 0 1 6 6 .9 5 7 1 9 6 .8 9 8 5 7 1 0 .0 0 0 0 0 2 3 0 .0 0 0 0 1 6 6 .9 5 7 1 2 3 0 .0 0 0 0 -9 1 .7 6 3 1 3 2 0 0 .0 0 0 0 3 0 .0 0 0 0 0 3 5 .0 0 0 0 0 1 6 6 .9 5 7 1 2 0 0 .0 0 0 0 -1 8 0 .0 7 2 8
P re ssure ba r 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 3 5 .4 6 3 7 5 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 3 5 .4 6 3 7 5 1 .4 9 5 8 8 3 2 .0 2 6 5 0 0 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0 2 .0 2 6 5 0 0 1 .0 1 3 2 5 0 1 .0 1 3 2 5 0
Va p o r F ra c 0 .0 1 .0 0 0 0 0 0 0 .0 0 .0 1 .0 0 0 0 0 0 1 .0 0 0 0 0 0 .1 0 7 9 1 4 7 0 .0 .7 4 2 6 6 9 9 1 .0 0 0 0 0 0 1 .0 0 0 0 0 0 1 .0 0 0 0 0 0 0 .0 1 .0 0 0 0 0 0
L iq uid F ra c 1 .0 0 0 0 0 02 .8 8 2 9 4 E-8 1 .0 0 0 0 0 0 1 .0 0 0 0 0 0 0 .0 2 .8 8 2 9 4 E-8 .8 9 2 0 8 5 3 1 .0 0 0 0 0 0 .2 5 7 3 3 0 1 0 .0 0 .0 0 .0 1 .0 0 0 0 0 0 0 .0
So lid F r a c 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0 0 .0
En tha lp y ca l /m o l -6 9 9 9 3 .5 3 -3 6 2 8 3 .7 4 -6 4 3 3 4 .2 1 -6 9 0 1 8 .0 7 -3 3 1 0 7 .3 4 -3 6 2 8 3 .7 4 -4 7 2 8 7 .4 8 -4 5 5 9 1 .3 7 -6 3 9 1 5 .0 9 2 2 1 0 .4 8 4 6 8 .0 0 2 6 2 -3 6 2 8 3 .7 4 4 6 1 0 2 .5 3 -1 4 4 0 .2 3 6
En tha lp y ca l /g m -3 4 9 7 .2 9 3 -7 0 5 .2 9 1 4 -9 3 7 .2 0 3 1 -3 8 3 1 .0 8 5 -7 9 6 .9 4 6 0 -7 0 5 .2 9 1 4 -5 8 7 .2 6 5 7 -1 0 9 7 .0 0 2 -7 6 0 .0 2 3 2 2 4 .0 2 4 1 1 2 .1 2 5 1 6 2 -7 0 5 .2 9 1 4 1 4 3 7 .7 3 9 -4 5 .0 0 9 0 7
En tha lp y ca l /se c -2 . 1 3 8 7 E+6 -6 7 4 2 1 .0 2 -4 . 1 6 1 7 E+6 -4 . 7 9 2 9 E+6-5 . 1 1 8 9 E+6-1 . 2 8 1 0 E+6-3 . 3 7 1 4 E+6-7 . 0 3 6 5 E+6 -3 . 5 5 0 8 E+6 6 1 4 0 2 .3 3 1 7 0 0 .0 6 6-1 . 3 4 8 4 E+61 .5 3 6 7 5 E+6 -4 0 0 .0 6 5 7
En tro p y ca l /m o l- K -3 8 .4 5 8 5 8 -8 .8 2 6 6 5 0 -6 1 .3 3 9 7 8 -4 1 .1 2 5 5 81 .5 7 5 6 9 E+9 -8 .8 2 6 6 5 0 -4 6 .7 2 1 4 9-2 . 1 1 2 E +1 0 -5 6 .4 9 6 4 30 .0 4 6 0 0 E+9 .2 2 6 0 8 2 7 -8 .8 2 6 6 5 0 5 .8 9 5 2 7 8 -8 .1 8 0 0 8 2

En tro p y ca l /g m -K -1 .9 2 1 6 2 0 -.1 7 1 5 7 4 4 -.8 9 3 5 8 1 0 -2 .2 8 2 8 1 2 .0 6 4 3 0 E+8 -.1 7 1 5 7 4 4 -.5 8 0 2 3 6 7-5 . 0 8 0 9 E+8 -.6 7 1 8 0 6 35 .3 1 0 4 7 E+7 7 .0 6 5 3 5 E-3 -.1 7 1 5 7 4 4 .1 8 3 8 4 8 2 -.2 5 5 6 3 7 2
De nsity m o l/cc .0 5 1 7 9 7 82 .7 9 0 5 6 E-5 .0 1 7 3 4 7 3 .0 5 5 9 6 9 82 .4 2 9 7 9 E-52 .7 9 0 5 6 E-55 .4 2 1 6 9 E-3 .0 3 2 1 6 7 9 7 .0 9 8 4 8 E-54 .0 7 4 9 6 E-53 .9 5 8 0 6 E-52 .7 9 0 5 6 E-5 .0 6 0 5 6 9 6 1 .3 4 7 0 9 E-4
De nsity g m /cc 1 .0 3 6 6 6 31 .4 3 5 6 0 E-3 1 .1 9 0 8 0 7 1 .0 0 8 3 1 21 .0 0 9 4 0 E-31 .4 3 5 6 0 E-3 .4 3 6 5 6 2 4 1 .3 3 6 8 9 7 5 .9 6 9 5 5 E-33 .7 4 9 4 2 E-31 .2 6 6 5 3 E-31 .4 3 5 6 0 E-3 1 .9 4 2 2 2 5 4 .3 1 0 5 2 E-3
Av e ra g e MW 2 0 .0 1 3 6 3 5 1 .4 4 5 0 3 6 8 .6 4 4 9 0 1 8 .0 1 5 2 8 4 1 .5 4 2 7 7 5 1 .4 4 5 0 3 8 0 .5 2 1 4 3 4 1 .5 5 9 9 5 8 4 .0 9 6 2 4 9 2 .0 1 1 0 8 3 1 .9 9 8 8 0 5 1 .4 4 5 0 3 3 2 .0 6 6 0 0 3 1 .9 9 8 8 0
L iq Vo l 6 0 F l/m in 3 3 .5 5 9 9 2 5 .6 5 8 4 3 3 0 .0 2 1 8 .5 5 2 9 7 5 .2 0 8 3 3 3 5 9 .4 4 8 2 1 0 7 .5 1 0 2 2 9 8 .1 6 1 6 3 5 8 .5 5 5 5 2 7 9 .7 8 3 3 1 0 6 .6 8 3 3 8 0 .3 3 6 7 0 1 1 3 .1 6 8 7 3 4 .8 4 0 6 0 0 .0 .8 9 2 6 3 0 0

DISCUSSION FOR ERRORS:

In the DMS column there is no convergence in the calculations and there is an error in
the distillate temperature and the condensate temperature.
In the DMSO column the feed pressure is less than the stage 2 pressure.
In the DMSO column the stages 3 and 4 were dried up due to which limit is imposed
in the flow rates in vapour-liquid or liquid vapour.

Conclusion:

The DMSO plant with feed rate of 100 kmole/hr is fed in the DMS reactor where the output
of DMSO (dimethyl sulfoxide) is of 26.2 K.mole/hr.

Uses of dmso:
As solvent in NMR studies as its having ability to dissolve a wide range of chemicals.
As a mild oxidant in organic synthesis
As a cryo-protectant, added to cell media to reduce ice formation and thereby prevent
cell death during the freezing process
As a drug vehicle in in-vivo and in-vitro experiments DMSO is metabolized to
dimethyl sulfone and dimethyl sulfide which is subjected to renal and pulmonary
excretion
In embolisation, the therapeutic occlusion of blood vessels as embolic agent

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 In veterinary medicine as a liniment for horses alone or combination with other
ingredients and other function of DMSO is as solvent to carry the other ingredients
across the skin
As an odourant in natural manufactured gas
As an intermediate in preparing many S-containing derivatives As a solvent for
spinning synthetic fibres such as polyacrylonitrile

REFERENCES:

1. Dryden's Outlines Of Chemical Technology by Rao , M Gopala

2. http://nptel.ac.in/courses/103106109/31-40/Lecture%2037%20Dimethyl%20sulfoxide.pdf
3. http://nptel.ac.in/courses/103106109/Block%20diagram/Dimethyl%20sulfoxide%20from%20
wood%20liquor(1).pdf
4. http://nptel.ac.in/courses/103106109/SWF%20files/Dimethyl%20sulfoxide%20from%20wood
%20liquor.swf

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