Project Nebula

BASIC ENGINEERING

WALK THROUGH REPORT

FOR
‘Galhueshield HCS’

Document Number
P90- TG59-014-002

Team members: Dilip Mhatre, Nikhil Deshmukh, Sarang, Palas Chattopadhyay, Suraj G
Location: W67, Tarapur
Date:09.01.2019

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 1 of 11

 Project Nebula
Walkthrough Information Gathering:

 Galhueshield HCS is a solid product. Galhueshield HCS has wide range of applications
due to its cationic nature such as Protects and retains applied hair color and imparts
sensorial properties Unique dry and wet sensory.
 Currently we are manufacturing Galhueshield HCS in W-67. It consists of 4 steps. First
three steps of Galhueshield & SunBeat are same.

 Step-1 Chlorination reaction (synthesis of RB-650)

a. Raw materials PMCA 1 mole (solid) & Catalyst D (0.25 % of acid) are charged
through manhole without stirring.
b. TC is charged from MS drum to charging receiver by using vacuum.
c. Thionyl chloride (1.05 mole) is added by maintaining 700-750 torr vacuum through
water jet ejector, Reaction is endothermic, during TC addition temperature is
dropped from room temperature to 0°C.
d. After complete TC addition reaction mass is heated up to 30°C & agitation is
started.
e. Reaction mass is digested for first 4 hours at 35 to 40°C and 2 hours at 60-65°C
under 700-750 torr using water jet ejector.
f. Then again digested for 2 hours at 78°C to 80°C under 0.1 to 0.5 torr using steam
jet ejector for vacuum.
g. Crude Base 650 is taken for distillation under 0.1 to 0.5 torr using steam ejector at
150-165°C.
h. Distilled RB 650 mass is unloaded in carboy having 50% MDC solution, to prepare
1:1 MDC & RB 650 mixture.

 Step-2 Amidification reaction (Synthesis of RB-700)

a. In this step MDC (25-27% on solid) & DMAPA are charged using AOD pump
(SS316) from drum.
b. Reaction mass is cooled to below 15°C.
c. MDC (50 %) is added in carbouy having Distilled RB650 mass 50 %, & prepared
1:1 MDC in RB 650 mixture. This mixture is prepared before 4 hours.
d. This mixture is charged in PP charging vessel by using vacuum.
e. Addition of solution of Base 650 & MDC (1:1 w/w) is started with maintaining temp
below 15°C.

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 2 of 11

 Project Nebula
f. After addition, stop cooling & digest reaction mass for 4 hours up to it attains room
temperature.
g. DM water (30% on solid) is used to extract RB-700 product from MDC layer.
Needs washing twice (70% & 30 % of total water) by DM water followed by
separation of the MDC and aqueous layer.
h. MDC is recovered from Aqueous layers in reactor by heating at 40-45 °C for 2
hours & 1 hours at 40-45°C under 0.5 torr. (We insure that whether all MDC is
recovered or not. If excess MDC (in PPM) from reaction is not recovered, then
Problem occurs in centrifuge for Separation. That’s why we do MDC recovery
under vacuum. If we increase temperature instead of applying vacuum, then
product gets decomposed & another unknown byproduct might get formed.
i. Caustic lye is added for getting pH 12-13 by maintaining temperature from 20°C to
25°C.After that cool reaction mass below 15°C & stir for 1 hour.
j. Mass is filtered by a Centrifuge & then cake is charged in reactor followed by 1:1
washing (to remove alkalinity) using water which is then followed by separation
using centrifuge.
k. RB700 cake is stored in 25-30 kg HDPE bag at room temperature.

 Step-3 Chlorination Reaction (Synthesis of Behenyl Chloride). -

a. Behenyl alcohol pellets (1mole) from bag & catalyst –D (0.5% on alcohol) from
HDPE drum are charged through manhole.
b. Reaction mass is heated up to 65 ̊ C with stirring under N2 blanketing (0.2 kg/cm2.)
c. After melting Behenyl alcohol ,730-750 torr Vacuum is applied by using water jet
ejector.

d. TC (1.05 mole) is charged from MS drum to charging receiver by using vacuum.

e. TC is added by maintaining temp 60-65 °C under 730-750 torr.

f. After completion of addition reaction mass is digested for 6 hours.
g. Sample is collected from reactor bottom valve, if Behenyl alcohol content is below-
1% then reaction mass is heated to 80 °C & apply full vacuum of water jet ejector
50-60 torr.
h. Traces of HCl & SO2, SOCl2 are removed at 80 ° C under full vacuum (0.1 torr) by
using steam jet ejector.
i. Reaction mass is cooled to room temperature & vacuum is break using nitrogen.

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 3 of 11

 Project Nebula
j. After completion of reaction Soda ash & water (1 :0.5 w/w) are added to remove
HCl & SO2.
k. Agitation done for 1 hour at 45 -50 °C and then kept for proper separation of two
layer.

l. Organic & aqueous layer gets separated and reaction mass is again charged for
second wash.
m. Applied plain water wash (1:0.5 w/w) to remove alkalinity. After that Agitation done
for 1 hour at 45-50 °C and then kept for proper separation of two layer.
n. Crude Behenyl chloride is unloaded in HDPE drum.
o. Crude Behenyl chloride is charged in SSR for distillation.

p. Vacuum is applied 0.1 to 0.3 torr using steam jet ejector.

q. Reaction mass heating is started using thermic fluid. (1st set point for thermic fluid
is 150°C) up to 130-150°C moisture is removed.
r. After removing of moisture reaction mass is heated up to 215-220°C by using
thermic fluid as a utility.
s. After distillation reactor bottom mass is drained in SS bucket.
t. Distilled Behenyl Chloride mass is unloaded in HDPE carbouy. It gets cooled to
the room temperature and it became solid (Solidification point 41°C), then it is
packed in bag.

 Step-5 Quaternization Reaction. (synthesis of Galhueshield HCS)

a. Behenyl chloride (1.01mole), DM water (on 30 % solid) & Galhueshield HCS (3%) are
charged through manhole.
b. Then N2 purging is started.
c. By keeping N2 purging RB 700 (1 mole) (solid) is charged through manhole.
d. Applied N2 pressure 0.2 kg/cm2 & the reaction mass is heated up to 120-125°C by using
steam.
e. At this temperature reactor pressure is observed 3 kg/cm2.
f. Reaction mass is digested for 12 hours.
g. After digestion reaction mass sample is collected from bottom valve of reactor. Amine %
is checked if it is not less than 1% then continue the digestion for 2 hours.
h. After achieving required result reaction mass is cooled to 70°C.

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 4 of 11

 Project Nebula
i. Reaction mass is unloaded in 50 kg HDPE carbouy. (Through nylon filter 5 micron) &
stored to room temperature.

Key Observations:

Existing Batch cycle time distribution for synthesis of Galhueshield BCT at W-67 is as follows:
1. Synthesis of RB 650
Description Time (min)
Ref. batch #12 ; 21.09.18
Product RB 650 105
Charging of PMCA & catalyst D 40
Addition of TC 155
heating Hot water circulation/ steam 45
Digestion 360
Heating up to 165°C 180
Distillation 1150
unloading 30
TOTAL 1960
Time for 106 kg RB650 32.7 Hrs.

2. Synthesis of RB 700
Description Time (min)
Ref. batch #04 ; 03.09.18
Charging of MDC & DAMAPA 60
Addition of RB-650 (dissolved in MDC) 540
Digestion 240
Addition of DM water(1st wash) 30
Settling & separation 60
Charging of MDC layer 30
Addition of DM water(2nd wash) 20
Settling & separation 60
Charging of Aq.layer 30
Heating & MDC recovery 540
Cooling up to RT 30

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 5 of 11

 Project Nebula
Addition of Caustic lye 30
cooling below 15 ̊C & maintaining 60
Filtration 420
Water wash (remove free Alkalinity) 60
Filtration & Packing 420
TOTAL 2630
Time for 170 Kg RB 700 43.8 hrs.

3. Synthesis of Behenyl Chloride

a. Behenyl chloride reaction
Description Time (min)
Ref. batch #02 ; 23.05.2016
Charging of Behenyl alcohol 60
Charging of Catalyst -D 30
Heating (in N2 blanketing) 120
Addition of TC 420
Digestion 520
Cooling up to RT 120
Washing twice 1.soda ash & plane wash 470
TOTAL 1740
Time for 106 Kg Crude Behenyl Chloride 29 hrs.

b. Behenyl chloride Distillation

Description Time (min)
Ref. batch #01 ; 10.05.2016
Charging of crude Behenyl chloride 30
Heating 240
Distillation 600
TOTAL 870
Time for 174 Kg Crude Behenyl Chloride 14.5 hrs

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 6 of 11

 Project Nebula
4. Synthesis of Galhueshield

Description Time (min)

Ref. batch #01 ; 13.05.2016
Charging of Behenyl chloride, DM water,
90
RB700 ,Galhueshield HCS
Apply N2 & Heating 150
Digestion 960
Cooling up to 70 ̊C 120
Packing 120
TOTAL 1440
Time for 1250 kg Galhueshield 24 hrs.

Time required to Synthesis of 1250 kg Galhueshield

Description Time (hrs.)

Synthesis of RB 650 (1 batch) 32.7
Synthesis of RB 700 (1 batch) 43.8
Synthesis of crude Behenyl Chloride Reaction (2 batch) 58
Synthesis of Behenyl Chloride Distillation (1 batch) 14.5
Synthesis of Galhueshield (1 batch) 24
Total Time for 1250 kg Galhueshield 173 hrs.

 During synthesis of RB 650 Stirring should not be started after charging of Cinnamic acid
powder & Catalyst D.
 Charging of solid RM to be done from manhole of the Reactor-Hazard analysis point
 Ensure reactor (RB650 & RB700) is fully dry if moisture is present in reactor then yield &
purity of product is reduced.
 PMCA free from moisture within limit.
 TC addition is critical & needs to be controlled (if TC addition rate is increased, rate of
generation of HCl & SO2 will increase drastically which can pressurize the vessel)
 In synthesis of RB700 step temperature should be maintained below 15°C to avoid
hydrolysis of RB-650

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 7 of 11

 Project Nebula
 Scrubber system is required during entire chlorination reaction to scrub out HCl, SO 2 &
unreacted SOCl2 gas. In existing set up we use steam jet ejector as a scrubber.
 Process needs the following Vacuum system:

a. RB650 Reaction-Water jet.

b. RB650 Distillation ORVP + Booster
c. MDC recovery -Steam Jet Ejector
d. Behenyl Chloride Reaction-water jet
e. Behenyl Chloride Distillation-ORVP+ Booster.
 In Quaternization reaction Nitrogen pressure 1 kg/cm2 (g) is must for pressurize & further
completion of the reaction.
 Temperature should not exceed more than 140°C for maintaining product color quality
 For sampling purpose double valve arrangement at the bottom is needed
 Vacuum system is most important for Recovery & distillation phase

 Equipment details

Equipmen Vacuum
Phase Capacity Agitator
t System
Anchor
Reaction GLR-2 160 Lit 1. Oil Ring
Step- blade
1 Vacuum Pump:
Anchor
Distillation GLR-2 160 Lit 350 m3/h
blade
Vacuum-0.1 torr
Anchor
reaction GLR-1 1000 Lit 2. Booster
blade
pump -1200
Step- MDC
SSR-1 1000 Lit Intermig m3/h. Vacuum-
2 recovery
0.1 torr
25 lit wet
Filtration Centrifuge NA 3. Steam Jet
cake
Ejector: 1800
Anchor
Step- Reaction GLR-2 160 Lit m3/h 3 stage
blade
3 steam jet and 1
Distillation SSR-4 200 Lit PBT
stage water jet.
Step- Vacuum-0.1 torr
Reaction SSR-1 1000 Lit Intermig
4

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 8 of 11

 Project Nebula
 All the fittings of electrical work must be flame proof
 N2 flushing system is available to avoid choking issue
 Reactor bottom valve must be steam jacketed

Problems/Fuguai in existing plant/system (if any):

 Need to focus on following areas during scale-up:

a. Distillation of Crude RB 650
b. Filtration Capacity
c. Vacuum system
 Filtration centrifuge capacity is insufficient. (ie-25 liter wet cake)
 For distillation heating capacity is insufficient. (GLR jacket is designed for 6 kg/cm 2 (g)
steam press. We required 9-10 kg/cm2 (g) steam press. For achieving the distillation
temperature during final stages)
 Heating with steam is insufficient.

Operator / staff interaction and feedback or suggestion (if any):

 In existing setup, we scrub HCl & SO2 gas through steam jet ejector. Scrubber system
provide during addition of Thionyl chloride for HCl & SO2 recovery.
 Heat tracing is required to RB 650 distilled & Behenyl chloride distilled mass collection
receiver.
 In existing distillation set up vacuum line found choked. So need to be a cleaning activity
of vacuum line in every 3 months.
 Currently we made mixture of RB650 & MDC in carbo/drum. Provide additional receiver
to preparing mixture of RB650.
 During filtration process more time consume due to small capacity of centrifuge. Increase
the capacity of centrifuge.

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 9 of 11

 Project Nebula
On-spot recommendations proposed by Walkthrough team

 N2 blanketing and N2 flushing line should be separate. As reactor volume is small in case
of pilot plant both the lines are same and cause no problem.
 During the Vacuum recovery of MDC sometimes happens that ORVP with booster
vacuum is not available due to use in some other products manufacturing and then we
have to go for water ejector vacuum. Hence, while designing Vacuum system for the
plant this point must be taken care of.
 MOC for the all equipment must be decided after checking compatibility only.
 In distillation of Behenyl chloride as temperature is a critical parameter there should be
two temperature sensors/ indicator for double check must be provided. At temperature
higher than 231°C then product degradation occurs.
 An additional tank and its respective pump to be provided for ease in charging of
aqueous layer during MDC recovery.

Summary and conclusion of walkthrough

 Galhueshield HCS synthesis consists of 4 steps:
1. Synthesis of RB-650
2. Synthesis of RB-700
3. Synthesis of Behenyl Chloride
4. Synthesis of Galhueshield HCS
 All the points will be considered while designing the plant.

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 10 of 11

 Project Nebula
Abbreviation

1. FBD-Fluidized Bed Dryer

2. PMCA-para Methoxy Cinnamic acid
3. TC-Thionyl Chloride
4. ORVP –Oil Ring vacuum pump
5. RB- Refined Base
6. MDC-Dichloromethane
7. DMAPA - 3-Dimethylaminopropylamine
8. SMBS – Sodium Metabisulfite
9. EDTA – Ethylene Diamine Tetra Acetic acid
10. BCT – Batch Cycle Time
11. RT-Room temperature
12. MOC- Material of Construction

NPT/SOP/PBE/009/F01 Rev No. 00 Effective date: 15/11/2017 Page 11 of 11