1. VIII INTERNATIONAL FORUM ON INDUSTRIAL SAFETYVIII INTERNATIONAL FORUM ON INDUSTRIAL SAFETY
Saint Petersburg 24Saint Petersburg 24 –– 27 May 201027 May 2010
““SafeSafe mmanagementanagement of an industrial process includingof an industrial process including
exothermic reactions and gaseous ammonia generationexothermic reactions and gaseous ammonia generation””
Giorgio Mari, Roberto Lauri
Italian National institute for safety and health, Roma, Italy (www.ispesl.it)
Carmela Metaponte
Pharmacy Faculty, University of Rome “La Sapienza”
Viro Romani
Biosint, Via del Murillo, 16, Sermoneta, Italy
УправлениеУправление безопасностьюбезопасностью производственногопроизводственного процессапроцесса,, включающеговключающего
экзотермическиеэкзотермические реакцииреакции ии выделениевыделение паровпаров аммиакааммиака
ДжорджиоДжорджио МариМари,, инженеринженер
ГосударственныйГосударственный институтинститут ИталииИталии попо вопросамвопросам безопасностибезопасности трудатруда ((ИталияИталия))
2. OVERVIEW OF THE PROBLEM
GENERAL DESCRIPTION OF THE METHOD
CHEMISTRY
STUDY OF THE PROCESS BY REACTION CALORIMETER
MASS AND ENERGY BALANCE
SCALE-UP TO INDUSTRIAL SIZE
REASONING OF: QUALITY – ECONOMY; SAFETY; ENVIRONMENT
PROCESS SEQUENCE
EXISTING REACTOR CHOICE AND PLANT ADJUSTMENT
DESCRIPTION OF SOME TECHNICAL SOLUTIONS IN THE PLANT
CONCLUSIONS
3. EUROPEAN COUNCIL DIRECTIVES 96/82/EC +EUROPEAN COUNCIL DIRECTIVES 96/82/EC +
2003/105/EC ON THE CONTROL OF MAJOR2003/105/EC ON THE CONTROL OF MAJOR--
ACCIDENT HAZARDS INVOLVINGACCIDENT HAZARDS INVOLVING
DANGEROUS SUBSTANCES (SEVESO)DANGEROUS SUBSTANCES (SEVESO)
AUTHORIZATION
INSPECTIONS (PERIOD ABOUT 2 YEARS)
SAFETY REPORT
SAFETY MANAGEMENT SYSTEM
INSPECTION COMMITTEE (3 people)
Ministry for the Environment
Fire Brigades
Institute for Safety and Health
4. CONVERSION OF THE HYDROCHLORIDE REACTANTCONVERSION OF THE HYDROCHLORIDE REACTANT ““AA”” TO BASETO BASE
BENZODIAZEPINE DERIVATE USED AS AN ANXIOLYTICBENZODIAZEPINE DERIVATE USED AS AN ANXIOLYTIC
8. REACTION CALORIMETER USED FOR THE PROCESS STUDYREACTION CALORIMETER USED FOR THE PROCESS STUDY
((MettlerMettler Toledo RC1)Toledo RC1)
9. TRIALS PERFORMED USING 2 LITRESTRIALS PERFORMED USING 2 LITRES
SIMULATION OF THE CONDENSERSIMULATION OF THE CONDENSER
SIMULATION OF THE AMMONIA TREATMENTSIMULATION OF THE AMMONIA TREATMENT
CONTINUOUS ADDITION OF REACTANTS ISCONTINUOUS ADDITION OF REACTANTS IS
SIMULATED IN SMALL STEPSSIMULATED IN SMALL STEPS
CATALYST (LiNHCATALYST (LiNH22) DESTRUCTION IS SIMULATED) DESTRUCTION IS SIMULATED
ENERGY BALANCEENERGY BALANCE
AGITATION IS CONSIDEREDAGITATION IS CONSIDERED
ADDITION OFADDITION OF ““COLDCOLD”” REACTANTS IS CONSIDEREDREACTANTS IS CONSIDERED
THERMAL DISPERSION OF THE CALORIMETER ISTHERMAL DISPERSION OF THE CALORIMETER IS
CONSIDEREDCONSIDERED
THERMAL LOSS DUE TO THE CONDENSATION IS NOTTHERMAL LOSS DUE TO THE CONDENSATION IS NOT
AUTOMATICALLY CONSIDEREDAUTOMATICALLY CONSIDERED
CALORIMETRIC TRIALSCALORIMETRIC TRIALS
10. GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALS
Batch and jacket temperatures chart during reactants (“A” + “B”) addition
11. GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALS
Heat generation chart during reactants (“A” + “B”) addition
Discovered Slightly Exothermic: 12 kJ/kg reagents
12. GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALS
Heat generation chart during catalyst (LiNH2) excess destruction
Discovered Exothermic: 53 kJ/kg water
13. INDUSTRIAL BATCHINDUSTRIAL BATCH
MASS AND ENERGY BALANCES WERE CALCULATEDMASS AND ENERGY BALANCES WERE CALCULATED
REACTOR: 3500 LITRESREACTOR: 3500 LITRES
SEVERAL PROBLEMS OF PHASES (WATERSEVERAL PROBLEMS OF PHASES (WATER VSVS. SOLVENT). SOLVENT)
CHANGES, SEPARATIONS, SUSPENTIONSCHANGES, SEPARATIONS, SUSPENTIONS
““AA””++””BB”” REACTANTS MIXTURE IS PREPARED IN ANHYDROUSREACTANTS MIXTURE IS PREPARED IN ANHYDROUS
SOLVENT (IN ABSENCE OF CATALYST NO REACTION HAPPENS)SOLVENT (IN ABSENCE OF CATALYST NO REACTION HAPPENS)
““AA””++””BB”” ARE TRANSFERRED IN A TANKARE TRANSFERRED IN A TANK
CATALYST SOLUTION PREPARATION IN THE REACTORCATALYST SOLUTION PREPARATION IN THE REACTOR
REACTION TEMPERATURE: 80REACTION TEMPERATURE: 80°°C (TRIALS AT 110C (TRIALS AT 110 °°C)C)
““AA””++””BB”” ADDITION IN THE REACTOR IS SLOW AND GRADUALADDITION IN THE REACTOR IS SLOW AND GRADUAL
RESIDUAL CATALYST (LiNHRESIDUAL CATALYST (LiNH22 ) DESTRUCTION IS ACHIEVED BY A) DESTRUCTION IS ACHIEVED BY A
SLOW WATER ADDITIONSLOW WATER ADDITION
14. -1200 lt“A”+”B” transferred
in a tank
“A”+”B” unloaded
Atm+4-200 kg“B” load
-900 mmHg+45Evaporated solvent
is dropped in
reactor
Residual water
< 0.1% Karl Fisher
water is completely
removed
Solvent evaporation and
condensation
Atm+4-300 ltLoading and further
separation of
demi water
2° washing
Atm+4-300 ltLoading and further
separation of
demi water
1° washing
-Aqueous phase
unloading
Phases separation through
decantation
Atm+4-700 kg“A” disolvs in the
solvent
Solvent load
-“A” in suspension“A” conversion to “base”
Atm+4-300 lt-Caustic soda 20% load
Atm+4-170 kg
(powder)
-“A” Hydrochloride load
Atm+ 4-200 lt-Demineralized water load
AtmAmbAirGaseous Nitrogen-Nitrogen padding
pressureT
°C
VentMaterial movedNotesProcess step
15. Atm+25-Aqueous phase
containing the
product (250 kg)
Decantation + filtrationDecantation and separation of
the aqueous phase
Atm+25-Demi water 160 lt
HCl 15%
“C” becomes
Hydrochloride and
disolves in the
aqueous phase
Conversion of “C”
5 mmHg abs+70Solvente + “A”
condensation
and removal
Solvent + “A”Precise Pressure trendReactant “A” excess distillation
FINISH
60 mmHg abs+50Solvente + “A”
condensation
and removal
Solvent + “A”“A” excess removal
(distillation)
Reactant “A” excess distillation
START
Atm+30Water + salts
300 lt
((decantationdecantation))2° Aqueous phase Elimination
Atm+30-Demi water
300 lt
Further washing2° Salts “washing”
Atm+30Water + salts
300 lt
((decantationdecantation))1° Aqueous phase Elimination
Atm+50-Demi water
150 lt
Salts disolve in the
aqueous phase
1° Salts “washing”
Atm+50NH3 to treatmentDemi water
150 litres
@ 50 lt/h
Generation of LiOH
and NH3
Catalyst (Lithium amide) excess
destruction
Atm+80NH3 to treatment
(solvent
condensation)
1200 lt
@ 300 lt/h
Alkylation ReactionReactants continuous addition in
the reactor
Atm+4-25 kgCatalystCatalyst LiNH2 load
Atm+4-400 ltDry solvent load
pressureT
°C
VentMaterial movedNotesProcess step
19. GLASS LINED BAFFLE
CROSS SECTION “C” SHAPED
. (CEPП) – good for suspensions
pH MEASURE
MEMBRANE PUMP
TEMPERATURE MEASURE
NITROGEN BUBBLING
SAFE SAMPLING
20. REACTANTSREACTANTS ““AA””++””BB”” ARE GRADUALLY ADDED IN THE REACTOR.ARE GRADUALLY ADDED IN THE REACTOR.
A PUNCTUAL AND GRADUAL ADDITION OF THEM IS ENSURED BY A PROPERA PUNCTUAL AND GRADUAL ADDITION OF THEM IS ENSURED BY A PROPER
INSTRUMENTATIONINSTRUMENTATION
PRESSURE CONTROL ON THE
PUMP DISCHARGE BY FREQUENCY
VARIATOR (INVERTER)
FLOWRATE IS CONTROLED BY A
MASS-FLOW-METER AND A CONTROL
VALVE (FACILITATED BY THE
CONSTANT PRESSURE)
21. GASEOUS AMMONIA HAS TO BE REMOVED AS MUCH AS POSSIBLE
SOLVENT HAS TO BE CONDENSED AS MUCH AS POSSIBLE
AMMONIA IS MORE SOLUBLE IN THE COLD SOLVENT !!!
!!
CONDENSATION IS DONE AT 2 DIFFERENT TEMPERATURES (+40CONDENSATION IS DONE AT 2 DIFFERENT TEMPERATURES (+40°°CC
AND THEN +5AND THEN +5°°C) IN ORDER TO MAXIMIZE THE AMMONIA REMOVALC) IN ORDER TO MAXIMIZE THE AMMONIA REMOVAL
FROM THE BATCHFROM THE BATCH
AT THE SAME TIME A GOOD CONDENSATION OF THE SOLVENT ISAT THE SAME TIME A GOOD CONDENSATION OF THE SOLVENT IS
ACHIEVEDACHIEVED
2 CONDENSATORS IN SERIES OPERATE AT +40 AND +52 CONDENSATORS IN SERIES OPERATE AT +40 AND +5°°CC
22. PROCESS IS MANAGED INPROCESS IS MANAGED IN
ORDER TO ENSURE ANORDER TO ENSURE AN
OUTLET AMMONIAOUTLET AMMONIA
FLOWRATE, WHICH ALLOWSFLOWRATE, WHICH ALLOWS
A PROPER OPERATION OFA PROPER OPERATION OF
THE ABSORPTION COLUMNSTHE ABSORPTION COLUMNS
REACTANTS “A”+”B” ARE
GRADUALLY ADDED IN THE
REACTOR
CONTROLLED AND GRADUAL
DESTRUCTION OF LITHIO AMIDE
AMMONIA CONVERTION TO
AMMONIUM SULPHATE
23. CONCLUSIONSCONCLUSIONS
POTENTIALLY DANGEROUS PROCESS
METHOD FOLLOWED
DETAILED STUDY OF THE PROCESS BY CALORIMETRIC
TRIALS.
TRIALS ARE PERFORMED WITH A QUANTITY WHICH
ALLOWS A REALISTIC SIMULATION OF THE INDUSTRIAL
PROCESS
MASS AND ENERGY BALANCE CALCULATION
SCALE UP TO INDUSTRIAL PROCESS
SAFE TECHNICAL SOLUTION IN THE INDUSTRIAL PLANT
24. спасибоспасибо заза вниманиевнимание
Giorgio MariGiorgio Mari giorgio.mari@ispesl.itgiorgio.mari@ispesl.it
Roberto LauriRoberto Lauri
CarmelaCarmela MetaponteMetaponte
Viro RomaniViro Romani
