LIFE presentation - - LIFE-TRIALKYL

With the contribution of the LIFE Programme of the European Unionunder grant agreement LIFE14/ENV/IT/000346

LIFE-TRIALKYL “An innovative and sustainable continuous process for the development of high quality trialkyl phosphites”

Demonstrative workshop– ARESE, Pilot Plant facilityLIFE14/ENV/IT/000346

• The process consists in the reaction between PCl3 and Alkyl Alcohol (Buthanol, Methanol) to produce Tri alkyl Phosphite in presence of Ammonia and diluted in a solvent (MTBE). The Hydrogen chloride is captured by Ammonia to produce Ammonium Chloride

• The reaction is followed by a Filtration to separate the Tri-alkyl phosphite by the solid Ammonium chloride

• The tri Alkyl phosphite is than purified by distillation.

• The solvent recovered is recycled to the reactor

Pilot realization

Allocated in Arese

• New metallic structure in a dedicated area

Resolving various constraints:

• Safety requests

• Regulations and requests of the institutional entities

• Operations requirements

Pilot realization

• Reactor

• 200 litres• special stainless steel Hastelloy• Cooled chilled water to control

exothermic reaction• Conical shape in the bottom part to

support solid discharge• Internal tubes with static mixers. • Possibility to feed ammonia from

the bottom• Automatic control for raw material

loading

Pilot realization

• Filters • Two stainless steel nutsche filter to separate solid

ammonium chloride from tri-alkylphosphite and solvent (MTBE)

• Heated with steam

• Distillation column• 40 cm diameter, 4 meters height• Structured packing internal filling corresponding

to 4 plates to separate Tri-Alkylphosphite from solvent/Buthanol and other by-products

Pilot realization

6

• Storage tanks• 3 small storage tanks for raw

materials (PCl3/MTBE/Alcohol/)

• Control system• PLC for supervision

Pilot realization

The “numbers” of the pilot plant:

• 14 vessels and equipment

• More than 15 rotating equipment

• More than 400 metres of process piping

• More than 250 signals and alarms

• A complete automatic fire extinguishing system

Pilot realization

Industrial Phase

• Started in Q4 2018 and concluded in June 2019

• 2 operators + 1 start up coordinator full time working on the pilot

• 24 pilot test done in different conditions and plant configuration

• Split in 4 phases corresponding to different set up of the reactor

• 5 test performed with final plant setup

• 2 different alkyl phosphites campaigns (TBP and TMP)

Starts with several issues:

• Reaction occuring with low yield and very low continuity

• Not repetitive, fluctuating high temperature

• Low cooling efficiency

• Heterogeneous dispersion of the threephasicmixture

• Solid plugging static mixer

• No product conveying to the collecting chamber

Industrial Phase

Industrial PhaseCHANGES ON THE REACTION SYSTEM MADE IN THREE STEPS

• Direct injections of reagents from the top intothe static mixer to improve mixing efficacyand reaction efficiency, NH3 from the bottom

• Condensation of MTBE to avoid dispersionsand potential occurance of VOCs

• Controlled recirculation to ensure soliddispersion and wider direct contact surfaces

• continuous reinjection of the liquid phasesinto the static mixer and to better control the temperature

FINAL CONFIGURATION (IND. PHASE 4)

• Temperature and yield improved• Prolonged process stability• No plugging• Limited solvent loss

2

3Raw materialsloading

Ammonia NH3 (gas)

2

3 4

4

IND.PHASE 1 IND PHASE 2 IND PHASE 3 IND PHASE 4

final conf.

Industrial PhaseThe performance switch

Industrial Phase5 more representatives trials in the final configuration (phase 4)

Industrial Phase5 more representatives trials in the final configuration (phase 4)

14

• Product (TBP - TriBhutilPhosphyte) within the target of >90% of the theor. Quantity

• Secondary product (solid NH4Cl) within th target of >90% of the theor.quantity

• Stable reaction parameters and continuous process

5 more representatives trials in the final configuration (phase 4)

Thank you all very

much

for your attention

With the contribution of the LIFE Programme of the European Unionunder grant agreement LIFE14/ENV/IT/000346

With the contribution of the LIFE Programme of the European Unionunder grant agreement LIFE14/ENV/IT/000346

Analytical targets and LIFE Products Analysis

Action A1.2 – TARGETS

Trimethylphosphite

Triethylphosphite

Tributyl phosphite

Appearance Clear liquid Clear liquid Clear liquid

Colour (Apha)

Max 50 apha Max 50 apha Max 50 apha

TAN (expected typical value + target)

<1 ; target 0.5 max

<2; target 0.5 max

<2; target 0.5 max

GC purity target

>95% >95% >90%

Action B2.1 – Preliminary results of tests (batch A = TBPi)

relative concentration of di-butyl phosphite and tri-butyl phosphite (target) via GC

0,00%10,00%20,00%30,00%40,00%50,00%60,00%70,00%80,00%90,00%

100,00%DBHP-TBP realtive concentration in the batch samples

DBHP

TBP

sample batch 17

sample batch 12sample batch 6

Action B2.1 – Preliminary results of tests (batch A = TBPi)

Action B2.3 – Testing and fine tuning (batch A = TBPi)

Clorobutano DBHP TBPTributyl

phosphateTest n. 21

Lot 21220520190,21% 2,06% 97,42% 0,31%

Test n. 22 Lot 2229052019

0,71% 3,28% 95,30% 0,71%

Test n. 23 Lot 2330052019

1,23% 3,37% 93,83% 1,57%

BOILING POINT Butanol 118°CChlorobutane 78°C

Approx 302°C

Approx 333°C 289°C

Action B2.5 – Validation (batch A = TBPi)

Distillation of the last batches, gave a validation product Lot 1906990013 that meets targets

Tributyl phosphiteTARGET

Tributyl phosphitevalidation product

Appearance Clear liquid Clear liquid

Colour (Apha) Max 50 apha 10 apha

TAN (expected typical value + target)

<2; target 0.5 max 0,10

GC purity target >90% 92,7%

Action B2.5 – Validation (batch A = TBPi)

Tributyl phosphite validation product Lot 1906990013: clear colourless, 92,7% purity

Action B2.1 – Preliminary results of tests (batch B = TMPi)

GC analysis of the preliminary test on TMPi

MeOH TMP DMHP TMPOTest n.1 Lot 0112062019 8,6% 71,1% 2,4% 13,0%

Test n.2 Lot 0218062019 6,9% 75,2% 13,6% 4,4%

BOILING POINT 65°C 111°C 170°C 197°C

Action B2.1 – Preliminary results of tests (batch B = TMPi)

Trimethyl phosphiteTARGET

Trimethyl phosphiteTest n.2 Lot 0218062019

Appearance Clear liquid Clear liquid

Colour (Apha) Max 50 apha 200 (to be distilled)

TAN (expected typical value + target)

<1; target 0.5 max 0,25

GC purity target >95% To be assessed after distillation – 75% purity on the crude product

Thank you all very

much

for your attention

With the contribution of the LIFE Programme of the European Unionunder grant agreement LIFE14/ENV/IT/000346